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Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds

Liye Chen

Peng Ren

, and

Brad P. Carrow^*

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Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States

*[email protected]

Cite this: J. Am. Chem. Soc. 2016, 138, 20, 6392–6395

Publication Date (Web):May 10, 2016

https://doi.org/10.1021/jacs.6b03215

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Abstract

We report here the remarkable properties of PAd₃, a crystalline air-stable solid accessible through a scalable S_N1 reaction. Spectroscopic data reveal that PAd₃, benefiting from the polarizability inherent to large hydrocarbyl groups, exhibits unexpected electron releasing character that exceeds other alkylphosphines and falls within a range dominated by N-heterocyclic carbenes. Dramatic effects in catalysis are also enabled by PAd₃ during Suzuki–Miyaura cross-coupling of chloro(hetero)arenes (40 examples) at low Pd loading, including the late-stage functionalization of commercial drugs. Exceptional space-time yields are demonstrated for the syntheses of industrial precursors to valsartan and boscalid from chloroarenes with ∼2 × 10⁴ turnovers in 10 min.

The capacity of ancillary ligands to tune the activity, selectivity, and stability of homogeneous metal catalysts has played a central role in the development of many modern synthetic methods.(1) Phosphines constitute one of the most utilized among various ligand types due in large part to the sensitivity of the electron density and steric environment about phosphorus towards substituent perturbations. The many areas of synthetic chemistry that utilize organophosphines, including emerging fields such as organocatalysis,(2) bioorthogonal reactions,(3) nanomaterials,(4) polymerization,(5)and frustrated Lewis pairs,(6)could thus benefit from expansion of accessible stereoelectronic properties beyond classical boundaries. Several recent discoveries that highlight this potential include Alcarazo’s phosphine cations’ ability to greatly accelerate π-acid catalysis,(7) Radosevich’s T-shaped phosphines’ oxidative additions,(8) and Dielmann’s imidazolin-2-ylidenaminophosphines’ reversible CO₂ fixation.(9)

Another enabling aspect of organophosphine chemistry has been the development of quantitative descriptors of their electronic and steric properties such as Tolman’s electronic parameter (TEP) and cone angle, respectively,(10) which aid both in mechanistic understanding and prediction of reactivity. A typical response of the TEP to increased α-carbon branching in the homoleptic series P{C[(H)_3–n(CH₃)_n]}₃ (n = 0–3) can be seen in Figure 1a (open circles). Tolman rationalized such a trend as arising from steric repulsion of larger substituents, which raises the HOMO energy as phosphorus adopts a more planar geometry (Figure 1b). However, a curious enhancement in donor strength that is not readily explained by geometric effects is evident for phosphines that possess alkyl substituents at the more distant β-position (e.g., PBu₃ and PCy₃) rather than β-methyl groups (e.g., PEt₃ and P(i-Pr)₃). We report here the first synthesis of tri(1-adamantyl)phosphine (PAd₃), which appears to capitalize on this effect more than existing phosphines to access electron-releasing properties exceeding a boundary for organophosphines that has persisted over many decades.(11)

Figure 1. Examples of β–substituent effects on the (a) TEP and (b) geometry of homoleptic phosphines. (a) χ = ν_CO(A₁) – 2056.1 cm^–1 for Ni(CO)₃(PR₃). (b) From solid-state data for Au(PR₃)Cl.(12)

Numerous syntheses of phosphines with two 1-adamantyl (Ad) substituents have been developed, many of which have found wide success in catalysis.(13) Installation of a third hindered Ad group, however, has remained challenging. In fact, any tri-tert-alkylphosphine for which all β-carbon positions are alkyl rather than methyl groups is, to the best of our knowledge, unprecedented. We found that reaction of ClPAd₂ and AdMgBr in the presence of a CuI/LiBr catalyst(14) led to complete consumption of the electrophile over 15 h but gave only trace amounts of PAd₃ (1). This is consistent with a noncatalyzed S_N2 route attempted by Whitesides.(15) An alternative strategy (Scheme 1a) to forge the final hindered P–C bond in PAd₃ that proved surprisingly facile involved instead an S_N1 reaction with Ad cation.(16)A mixture of the commercial reagent HPAd₂, AdOAc (1.1 equiv), and Me₃SiOTf (1.2 equiv) cleanly generated protonated PAd₃ over 24 h at rt.(17) Neutralization of 1·HOTf with Et₃N formed a colorless precipitate, pure PAd₃, that was simply filtered under air in good yield (63%) on a multigram scale. We were surprised to then discover that negligible oxidation of solid PAd₃ occurred during storage under air over a period of three months, as determined from periodic analysis of aliquots by ³¹P NMR spectroscopy.(18) This behavior contrasts starkly with many other alkylphosphines that are air-sensitive and in the case of P(t-Bu)₃, pyrophoric.

Scheme 1. Synthesis and Properties of PAd₃ (1)

Comparison of the Charton steric parameter (υ) for the Ad group (1.33) compared to, for instance, a t-Bu group (1.24) intuitively suggests that PAd₃ should be more sterically hindered than other trialkylphosphines.(19) We thus synthesized (PAd₃)AuCl (2) (Scheme 1b) and the air-stable cationic complex 4, prepared in one step by coordination of 1 to palladacycle 3 (Scheme 1c),(20) to quantitatively establish the steric properties of PAd₃. The cone angle (θ) calculated from the solid-state structure of 2 (179°) is similar to the reported value for P(t-Bu)₃ (182°).(10b) Similarly, the buried volume parameter (%V_bur) of PAd₃ in 2 (40.5) calculated using the SambVca program(21) is close to that for P(t-Bu)₃ (40.0) in an analogous gold complex.(10b, 22) Values for PAd₃ in 4 (40.3) versus P(t-Bu)₃ in Pd[P(t-Bu)₃](Ph) (Br) (39.3)(23) are also similar. We thus conclude PAd₃ and P(t-Bu)₃ are best described as isosteric, which contrasts common proposals about the differences of Ad- and t-Bu-phosphine congeners.(24)

The electronic properties of PAd₃ (Scheme 1d) were next established from the carbonyl stretching frequency of 5 (ν_CO 1948.3 cm^–1), which occurs at a uniquely low frequency among alkylphosphines. Analogous Rh complexes (S3–S5) ligated by P(t-Bu)₃ (ν_CO 1956.4 cm^–1), PAd₂(n-Bu) (ν_CO 1956.9 cm^–1), or PCy₃ (ν_CO 1958.7 cm^–1) all exhibit distinctly higher frequencies indicative of reduced electron releasing ability of these compared to PAd₃.(25) The TEP for PAd₃ (2052.1 cm^–1), indirectly calculated from the relationship between ν_CO for Ni(CO)₃(L) and Rh(acac) (CO)(L) complexes (Figure S5),(26) is significantly red-shifted compared to P(t-Bu)₃(2056.1 cm^–1) and other alkylphosphines.(10a, 10c) In fact, PAd₃ approaches a range typical of N-heterocyclic carbenes (e.g., IPr; 2051.5 cm^–1)(27) that are generally regarded as superior σ donors to transition metals.(28) Additional theoretical and experimental data that corroborate this spectroscopic data include a higher calculated HOMO energy for PAd₃ (+0.20 eV) relative to P(t-Bu)₃, a larger pK_α^THF of the conjugate acid of PAd₃ (11.6) compared to P(t-Bu)₃(10.7),(29) and a smaller ¹J(³¹P-⁷⁷Se) coupling constant for Ad₃PSe (669.9 Hz) than for (t-Bu)₃PSe (688.2 Hz).(30)

Several effects were considered that might account for the unique electronic properties of PAd₃. The average C_α–C_β bond length of PAd₃ in 2 (1.551(4) Å) is slightly longer than the average C_β–C_γ (1.537(4) Å) and C_γ–C_δ (1.530(4) Å) bond lengths. A hyperconjugative effect would be expected to contract the C_α–C_β bonds,(31) which is clearly not the case. The sum of the C–P–C angles about PAd₃ (332.6(4)°) determined from solid-state data for 2 are slightly less compared to P(t-Bu)₃ in the analogous gold complex (335(3)°).(12a) The C–P–C angles in 4 and the known complex Pd[P(t-Bu)₃](Ph)(Br) are also similar.(20) These data show that planarization of phosphorus also does not account for the properties of PAd₃. However, London dispersion could explain the slight contraction of the C–P–C bond angles in PAd₃,(11) and this possibility led us to further consider van der Waals forces.(11, 32) The larger Taft polarizability parameter (σ_α) of Ad (− 0.95) compared to t-Bu (− 0.75) indicates the former is better able to facilitate electron donation from phosphorus by stabilizing a more polarized P–M dative bond.(33) In fact, a general correlation is observed between σ_α and the TEP of a series of homoleptic alkylphosphines (eq 1). This correlation suggests to us that van der Waals forces might account for the trend that phosphines possessing large β-alkyl groups are more electron-releasing than the β-methyl analogues (Figure 1a).(11)(1)

Because transition states are generally more polarizable than are ground states,(34) we wanted to assess effects of PAd₃ within a catalytic manifold. We chose as a challenging test case the room temperature Suzuki–Miyaura cross-coupling (SMC) of p-chloroanisole (0.50 mmol), 1-naphthylboronic acid (0.55 mmol), and KOH (1.1 mmol) in the presence of palladacycle 3 and a phosphine (0.05 mol % Pd; L/Pd = 1 in all cases) in THF/toluene (eq 2). The use of P(t-Bu)₃, PAd₂(n-Bu), or PCy₃, each of which is used extensively for SMC,(35) led to low yields (<10%) of 1-(p-anisyl)naphthalene (6) over 8 h (Figure 2). In contrast, the reaction catalyzed by the combination of 3 and PAd₃ under identical conditions proceeded to 99% yield within 4 h. The yield of 6 at 10 min (99%) using 0.25 mol % 3 and 0.5 mol % PAd₃ corresponds to a turnover frequency (TOF) of 1.2 × 10⁴ h^–1 at rt even with this quintessential deactivated substrate for SMC; an analogous reaction using P(t-Bu)₃ was slower and stalled at ∼33% yield (Figure S3). The reactivity of 3 and PAd₃ compared favorably even head-to-head against state-of-the-art precatalysts such as SPhos-Pd G2, XPhos-Pd G3, and PEPPSI-IPr.(36) Note that these data only sample the ensemble of ligand effects on catalyst initiation, innate reactivity, and stability that affect the overall catalyst performance. We do believe the high reactivity of the PAd₃-Pd catalyst in this SMC reflects the donicity and polarizability of PAd₃, but a related PAd₃-Pd complex (S1) was also found to be very stable toward cyclometalation (Figure S1). Thus, catalyst stability differences might also contribute to these observations.

Figure 2. Yield of 6 from reactions in eq 2. L/Pd = 1 in all cases.

The stark contrast of the catalytic effects of PAd₃ versus, for instance, PAd₂(n-Bu) in this SMC is surprising given the structural similarities. We considered that Tolman’s proposal of substituent additivity (eq 3)(10a) could be used to evaluate if in fact the number of Ad groups exerts a proportional effect on the phosphine properties. We thus determined χ_Ad (eq 4) in PAd₃ (− 1.3 cm^–1), PAd₂(n-Bu) (− 0.20 cm^–1), and PAd₂Bn (−1.0 cm^–1) using known χ_R and TEP values.(10a) The variance in χ_Ad indicates that, contrary to Tolman’s proposal,(10c) the influence of the Ad group is actually dependent on the exact phosphine structure and also that phosphorus apparently gains more electron density per Ad group in the case of PAd₃.(3)(4)

Lastly, we broadened our investigation of the SMC to establish if PAd₃-Pd catalysts might be broadly applicable at low Pd loading (≤0.1 mol %),(37) which is desirable for industrial applications yet remains challenging using chloroarenes.(38) A limited selection of solvents (THF, toluene, or n-BuOH) and bases (K₃PO₄ or K₂CO₃) using 4 as catalyst was sufficient to achieve high yields across 40 diverse combinations of chloro(hetero)arene and organoboronic acid. Representative examples are shown in Scheme 2 with the remainder listed in Figure S4. Complex 4 retained high activity in the presence of N-heteroaryl substrates including pyridine, pyrrole, pyrazine, pyrimidine, isoxazole, triazine, and thiadiazole fragments giving high yields within 1–12 h using 0.05–0.1 mol % [Pd]. Products from reactions with organoboron compounds that are notoriously sensitive to protodeboronation such as 2-pyrrolyl, 2-furyl, 2-thienyl, and 2,6-difluorophenyl boronic acids also formed in high yields even at low catalyst loadings.(39) Reactions that formed industrial precursors (7, 8) to valsartan and boscalid proceeded to high yield (95–97%) within 10 min at 100 °C using 0.005 mol % [Pd].(37b) These turnover numbers (TON) of ∼2 × 10⁴ and exceptional TOFs exceeding 1 × 10⁵h^–1 highlight that high space-time yield are accessible using less reactive chloroarenes and low Pd loading. High TON within 1–5 h are also observed for reactions of N-heteroarenes (9–11). Lastly, functionalization by SMC of the C–Cl bond in haloperidol, fenofibrate, montelukast, glibenclamide, and 5-R-rivaroxaban with methyl, cyclopropyl, heteroaromatic, or fluoroaromatic fragments occurred in uniformly good yields (65–92%). We were very encouraged by the observations that PAd₃, a simple compound readily prepared from inexpensive reagents, engenders catalytic properties rivaling some of the most important methods developed for SMC reactions.

Scheme 2. Illustrative Examples of 4 as a General Catalyst for Suzuki–Miyaura Coupling of Chloro(hetero)arenes^a

In conclusion, a facile and scalable synthesis of PAd₃ has been developed. Spectroscopic data reveal PAd₃ is significantly more donating than P(t-Bu)₃, thus redefining the limit of electron-releasing character accessible to alkylphosphines that has persisted for half a century. Preliminary investigations to establish how the electronic properties and chemical stability of PAd₃ might be leveraged revealed that a PAd₃-palladacycle catalyzes Suzuki–Miyaura coupling of chloro(hetero)arenes with exceptional TOF and high TON. A strong correlation between the Tolman electronic and Taft σ_α parameters argues the special properties of PAd₃ originate from the substantial polarizability inherent to large hydrocarbyl groups like adamantyl. These results support the hypothesis that access to phosphine steric or electronic properties beyond historical limits can enable unique reactivity in catalysis and also contribute to a growing number of examples for which weak van der Waals forces can in fact contribute significantly to both structure and reactivity.(11)

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Corresponding Author
- Brad P. Carrow - Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States; Email: [email protected]
Authors
- Liye Chen - Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
- Peng Ren - Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
Notes
The authors declare the following competing financial interest(s): A patent application was filed by Princeton University, which is not yet published.

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Financial support was provided by Princeton University. We thank Long Wang for efforts to characterize complexes of 1.

References

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Accounts of Chemical Research (2010), 43 (7), 1005-1018CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
A review. Catalytic asym. synthesis has received considerable attention over the past few decades, becoming a highly dynamic area of chem. research with significant contributions to the field of org. synthesis. In the development of new catalysts, the concept of multifunctional catalysis described by Shibasaki and co-workers, namely, the combination of more than one functional group within a single mol. to activate the transformation, has proved a powerful strategy in the design of efficient transition metal-contg. catalysts. A variety of reactions have since been addressed with multifunctional organocatalysts. One example is the Morita-Baylis-Hillman (MBH) reaction, in which a carbon-carbon bond is created between the α-position of an activated double-bond compd. and a carbon electrophile. The seminal report on this reaction in 1972 described the prototypical couplings of (i) Et acrylate with acetaldehyde and (ii) acrylonitrile with acetaldehyde; the reaction is promoted by the conjugate addn. of a nucleophilic catalyst to the α,β-unsatd. aldehyde. Many variations of the MBH reaction have been reported, such as the aza-MBH reaction, in which an N-tosyl imine stands in for acetaldehyde. Recent innovations include the development of chiral mols. that catalyze the prodn. of asym. products. In this Account, we describe the refinement of catalysts for the MBH and related reactions, highlighting a series of multifunctional chiral phosphines that we have developed and synthesized over the past decade. We also review similar catalysts developed by other groups. These multifunctional chiral phosphines, which contain Lewis basic and Bronsted acidic sites within one mol., provide good-to-excellent reactivities and stereoselectivities in the asym. aza-MBH reaction, the MBH reaction, and other related reactions. We demonstrate that the reactivities and enantioselectivities of these multifunctional chiral phosphines can be adjusted by enhancing the reactive center's nucleophilicity, which can be finely tuned by varying nearby hydrogen-bonding donors. Artificial catalysts now provide highly economic access to many desirable compds., but the general adaptability and reactivity of these platforms remain problematic, particularly in comparison to nature's catalysts, enzymes. The multifunctional organocatalysts described in this Account represent another pos. step in the synthetic chemist's efforts to profitably mimic nature's catalytic platform, helping develop small-mol. catalysts with enzyme-like reactivities and selectivities.
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(b) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535 DOI: 10.1021/ar000253x
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Reactions of Electron-Deficient Alkynes and Allenes under Phosphine Catalysis
Lu, Xiyan; Zhang, Chunming; Xu, Zhenrong
Accounts of Chemical Research (2001), 34 (7), 535-544CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
The development of some new synthetic reactions derived from nucleophilic addn. of phosphines to electron-deficient carbon-carbon triple bonds is reviewed with 40 refs. These reactions show that the phosphine plays the role of a nucleophile as well as an excellent leaving group. The central problem is to generate a 1,3-dipole from alkynoates or allenoates (2,3-butadienoates) by interaction with various phosphines. This study illuminates the unusual phenomena and shows how this understanding allows control of the reaction.
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3
Sletten, E. M.; Bertozzi, C. R. Acc. Chem. Res. 2011, 44, 666 DOI: 10.1021/ar200148z
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3
From Mechanism to Mouse: A Tale of Two Bioorthogonal Reactions
Sletten, Ellen M.; Bertozzi, Carolyn R.
Accounts of Chemical Research (2011), 44 (9), 666-676CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
A review. Bioorthogonal reactions are chem. reactions that neither interact with nor interfere with a biol. system. The participating functional groups must be inert to biol. moieties, must selectively reactive with each other under biocompatible conditions, and, for in vivo applications, must be nontoxic to cells and organisms. Addnl., it is helpful if one reactive group is small and therefore minimally perturbing of a biomol. into which it has been introduced either chem. or biosynthetically. Examples from the past decade suggest that a promising strategy for bioorthogonal reaction development begins with an anal. of functional group and reactivity space outside those defined by Nature. Issues such as stability of reactants and products (particularly in water), kinetics, and unwanted side reactivity with biofunctionalities must be addressed, ideally guided by detailed mechanistic studies. Finally, the reaction must be tested in a variety of environments, escalating from aq. media to biomol. solns. to cultured cells and, for the most optimized transformations, to live organisms. Work in our lab. led to the development of two bioorthogonal transformations that exploit the azide as a small, abiotic, and bioinert reaction partner: the Staudinger ligation and strain-promoted azide-alkyne cycloaddn. The Staudinger ligation is based on the classic Staudinger redn. of azides with triarylphosphines first reported in 1919. In the ligation reaction, the intermediate aza-ylide undergoes intramol. reaction with an ester, forming an amide bond faster than aza-ylide hydrolysis would otherwise occur in water. The Staudinger ligation is highly selective and reliably forms its product in environs as demanding as live mice. However, the Staudinger ligation has some liabilities, such as the propensity of phosphine reagents to undergo air oxidn. and the relatively slow kinetics of the reaction. The Staudinger ligation takes advantage of the electrophilicity of the azide; however, the azide can also participate in cycloaddn. reactions. In 1961, Wittig and Krebs noted that the strained, cyclic alkyne cyclooctyne reacts violently when combined neat with Ph azide, forming a triazole product by 1,3-dipolar cycloaddn. This observation stood in stark contrast to the slow kinetics assocd. with 1,3-dipolar cycloaddn. of azides with unstrained, linear alkynes, the conventional Huisgen process. Notably, the reaction of azides with terminal alkynes can be accelerated dramatically by copper catalysis (this highly popular Cu-catalyzed azide-alkyne cycloaddn. (CuAAC) is a quintessential "click" reaction). However, the copper catalysts are too cytotoxic for long-term exposure with live cells or organisms. Thus, for applications of bioorthogonal chem. in living systems, we built upon Wittig and Krebs' observation with the design of cyclooctyne reagents that react rapidly and selectively with biomol.-assocd. azides. This strain-promoted azide-alkyne cycloaddn. is often referred to as "Cu-free click chem.". Mechanistic and theor. studies inspired the design of a series of cyclooctyne compds. bearing fluorine substituents, fused rings, and judiciously situated heteroatoms, with the goals of optimizing azide cycloaddn. kinetics, stability, soly., and pharmacokinetic properties. Cyclooctyne reagents have now been used for labeling azide-modified biomols. on cultured cells and in live Caenorhabditis elegans, zebrafish, and mice. As this special issue testifies, the field of bioorthogonal chem. is firmly established as a challenging frontier of reaction methodol. and an important new instrument for biol. discovery. The above reactions, as well as several newcomers with bioorthogonal attributes, have enabled the high-precision chem. modification of biomols. in vitro, as well as real-time visualization of mols. and processes in cells and live organisms. The consequence is an impressive body of new knowledge and technol., amassed using a relatively small bioorthogonal reaction compendium. Expansion of this toolkit, an effort that is already well underway, is an important objective for chemists and biologists alike.
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4
(a) Kim, S.; Lim, Y. T.; Soltesz, E. G.; De Grand, A. M.; Lee, J.; Nakayama, A.; Parker, J. A.; Mihaljevic, T.; Laurence, R. G.; Dor, D. M.; Cohn, L. H.; Bawendi, M. G.; Frangioni, J. V. Nat. Biotechnol. 2004, 22, 93 DOI: 10.1038/nbt920
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Myers, M.; Connor, E. F.; Glauser, T.; Möck, A.; Nyce, G.; Hedrick, J. L. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 844 DOI: 10.1002/pola.10168.abs
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Phosphines: nucleophilic organic catalysts for the controlled ring-opening polymerization of lactides
Myers, Matthew; Connor, Eric F.; Glauser, Thierry; Mock, Andreas; Nyce, Gregory; Hedrick, James L.
Journal of Polymer Science, Part A: Polymer Chemistry (2002), 40 (7), 844-851CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)
A new metal-free synthetic approach to the controlled ring-opening polymn. (ROP) of lactide with nucleophilic phosphines as transesterification catalysts is described. P(Bu)3, PhPMe2, Ph2PMe, PPh3, and related phosphines are com. available, inexpensive catalysts that generate narrowly dispersed polylactides with predictable mol. wts. These org. catalysts must be used in combination with an initiator, such as an alc., to generate an alcoholate ester α-end group upon ROP. A likely polymn. pathway is through a monomer-activated mechanism, with minimal active species, facilitating narrow mol. wt. distributions.
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Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2010, 49, 46 DOI: 10.1002/anie.200903708
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Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
Stephan, Douglas W.; Erker, Gerhard
Angewandte Chemie, International Edition (2010), 49 (1), 46-76CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
A review. Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form classical Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically frustrated Lewis pairs (FLPs) is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramol. combinations of bulky phosphines or amines with strongly electrophilic RB(C6F5)2 components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H+/H- pairs (stabilized for example, as the resp. phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small mols., including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chem.
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Petuškova, J.; Patil, M.; Holle, S.; Lehmann, C. W.; Thiel, W.; Alcarazo, M. J. Am. Chem. Soc. 2011, 133, 20758 DOI: 10.1021/ja210223s
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Dunn, N. L.; Ha, M.; Radosevich, A. T. J. Am. Chem. Soc. 2012, 134, 11330 DOI: 10.1021/ja302963p
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Main Group Redox Catalysis: Reversible PIII/PV Redox Cycling at a Phosphorus Platform
Dunn, Nicole L.; Ha, Minji; Radosevich, Alexander T.
Journal of the American Chemical Society (2012), 134 (28), 11330-11333CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
A planar, trivalent phosphorus compd. is shown to undergo reversible two-electron redox cycling (PIII/PV) enabling its use as catalyst for a transfer hydrogenation reaction. The trivalent phosphorus compd. activates ammonia-borane to furnish a 10-P-5 dihydridophosphorane, which in turn is shown to transfer hydrogen cleanly to azobenzene, yielding diphenylhydrazine and regenerating the initial trivalent phosphorus species. This result constitutes a rare example of two-electron redox catalysis at a main group compd. and suggests broader potential for this nonmetal platform to support bond-modifying redox catalysis dominated by transition metal catalysts.
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(a) Buß, F.; Mehlmann, P.; Mück-Lichtenfeld, C.; Bergander, K.; Dielmann, F. J. Am. Chem. Soc. 2016, 138, 1840 DOI: 10.1021/jacs.5b13116
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Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis
Tolman, Chadwick A.
Chemical Reviews (Washington, DC, United States) (1977), 77 (3), 313-48CODEN: CHREAY; ISSN:0009-2665.
A review, with 298 refs.
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Substituent effect on the basicity of phosphorus ligands in R3P-Ni(CO)3 complexes
Bartik, T.; Himmler, T.; Schulte, H. G.; Seevogel, K.
Journal of Organometallic Chemistry (1984), 272 (1), 29-41CODEN: JORCAI; ISSN:0022-328X.
According to Tolman, the χ values of P ligands can be detd. exactly by Fourier transform IR spectroscopy (FTχ values). By replacing the Ph groups of PPh3 by alkyl or alkoxy substituents, giving 157 P ligands, it was found that Tolman's additivity rule is not strictly valid. The deviations from the additivity rule were controlled by the donor-acceptor properties of the atoms bonded to P. Thus, substituents with nearly the same FTΧi parameters, such as OMe vs. SPh or CMe3 vs. SiMe3, but different influences on reactivity (activation vs. inhibition) can be recognized.
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London Dispersion in Molecular Chemistry-Reconsidering Steric Effects
Wagner, J. Philipp; Schreiner, Peter R.
Angewandte Chemie, International Edition (2015), 54 (42), 12274-12296CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
A review. London dispersion, which constitutes the attractive part of the famous van der Waals potential, has long been underappreciated in mol. chem. as an important element of structural stability, and thus affects chem. reactivity and catalysis. This negligence is due to the common notion that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly and can amt. to tens of kcal mol-1. This Review collects and emphasizes the importance of inter- and intramol. dispersion for mols. consisting mostly of first row atoms. The synergy of expt. and theory has now reached a stage where dispersion effects can be examd. in fine detail. This forces us to reconsider our perception of steric hindrance and stereoelectronic effects. The quantitation of dispersion energy donors will improve our ability to design sophisticated mol. structures and much better catalysts.
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Crystal structures of chloro(trimethylphosphine)gold(I), chloro(triisopropylphosphine)gold(I) and bis(trimethylphosphine)gold(I) chloride
Angermaier, Klaus; Zeller, Edgar; Schmidbaur, Hubert
Journal of Organometallic Chemistry (1994), 472 (1-2), 371-6CODEN: JORCAI; ISSN:0022-328X.
The crystal structures of chloro(trimethylphosphine)gold(I) (I), chloro(triisopropylphosphine)gold(I) (II), and bis(trimethylphosphine)gold(I) chloride·2CHCl3 (III) were detd. by single crystal x-ray diffraction studies. At. coordinates are given. I is triclinic, space group P‾1; II is orthorhombic, space group Pna21; and III is tetragonal, space group P‾4. The monomeric units of the mol. complexes I and II have linear P-Au-Cl axes. However, the monomers of I are aggregated to form a helical chain through fairly short alternating Au...Au contacts of 327.1(1), 335.6(1), and 338.6(1) pm and Au-Au-Au angles of 141.6(1), 141.8(1) and 141.9(1)°. By contrast, the monomers of II show no such Au...Au contacts in the lattice. This distinction between the 2 structures of the 2 analogous species is attributed to the different steric requirements of the phosphines. The crystals of III consist of layers of (Me3P)2AuCl complexes sepd. by layers of solvent mols. The P-Au-P coordination is almost linear, with a Cl atom at right angles (Au-Cl 316.7(1) pm, Cl-Au-P 92.3(1)°).
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Dichlorophosphonites and chlorophosphinates containing an adamantane fragment
No, B. I.; Zotov, Yu. L.; Karev, V. N.
Zhurnal Obshchei Khimii (1990), 60 (8), 1795-9CODEN: ZOKHA4; ISSN:0044-460X.
Reaction of adamantane or 1,3-dimethyladamantane with PCl3 in the presence of AlCl3 gave 94-95% R2P(O)Cl (I; R = adamantyl, 3,5-dimethyl-1-adamantyl).. Redn. of I (R = adamantyl) (II) with LiAlH4 gave 62% R2PH, which upon air oxidn. gave 90% R2P(O)H. Treating II with Br2 and AlBr3 gave 81% I (R = 3-bromo-1-adamantyl).
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Di-1-adamantylphosphine, a highly sterically hindered phosphine. Preparation and reactions
Goerlich, Jens R.; Schmutzler, Reinhard
Phosphorus, Sulfur and Silicon and the Related Elements (1993), 81 (1-4), 141-8CODEN: PSSLEC; ISSN:1042-6507.
Di-1-adamantylphosphine [(1-Ad)2PH] 1 was synthesized by redn. of (1-Ad)2P(O)Cl with LiAlH4 or HSiCl3. The reaction of 1 with H2O2, elemental sulfur and selenium afforded the corresponding secondary phosphine oxides, sulfides and selenides, (1-Ad)2P(X)H (X = O, S, Se). In the reaction of 1 with two equiv of Me3SiN3 oxidn. occurred with formation of (1-Ad)2P(:NSiMe3)NHSiMe3 6. Despite the steric hindrance, MeI quaternized the P-atom in 1 to give [(1-Ad)2PHMe]I 7. The phosphine (1-Ad)2PMe 8 was formed in the reaction of 7 with NEt3 and was oxidized by O2 to give (1-Ad)2P(O)Me 9.
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The stability of pure 1 may be related to its crystallinity (mp 357 °C, dec), because a solution of 1 does oxidize when exposed to air.
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(a) Müller, T.; Mingos, D. M. Transition Met. Chem. 1995, 20, 533 DOI: 10.1007/BF00136415
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Mueller, Thomas E.; Mingos, D. Michael P.
Transition Metal Chemistry (London) (1995), 20 (6), 533-9CODEN: TMCHDN; ISSN:0340-4285. (Chapman & Hall)
A new method of evaluating the Tolman cone angle from x-ray structural data available from the Cambridge Crystallog. Data Base was developed and a statistical anal. of the cone angles of the phosphines PPh3, PMe2Ph, PMePh2, PMe3, PEt3 and PCy3 (Cy = cyclohexyl) in transition metal complexes was completed.
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Percent buried volume for phosphine and N-heterocyclic carbene ligands: steric properties in organometallic chemistry
Clavier, Herve; Nolan, Steven P.
Chemical Communications (Cambridge, United Kingdom) (2010), 46 (6), 841-861CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
A review. Electronic and steric ligand effects both play major roles in organometallic chem. and consequently in metal-mediated catalysis. Quantifying such parameters is of interest to better understand not only the parameters governing catalyst performance but also reaction mechanisms. Nowadays, ligand mol. architectures are becoming significantly more elaborate and existing models describing ligand sterics prove lacking. This review presents the development of a more general method to det. the steric parameter of organometallic ligands. Two case studies are presented: the tertiary phosphines and the N-heterocyclic carbenes.
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A New Palladium Precatalyst Allows for the Fast Suzuki-Miyaura Coupling Reactions of Unstable Polyfluorophenyl and 2-Heteroaryl Boronic Acids
Kinzel, Tom; Zhang, Yong; Buchwald, Stephen L.
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Boronic acids which quickly deboronate under basic conditions, such as polyfluorophenylboronic acid and five-membered 2-heteroarom. boronic acids, are esp. challenging coupling partners for Suzuki-Miyaura reactions. Nevertheless, being able to use these substrates is highly desirable for a no. of applications. Having found that monodentate biarylphosphine ligands can promote these coupling processes, we developed a precatalyst that forms the catalytically active species under conditions where boronic acid decompn. is slow. With this precatalyst, Suzuki-Miyaura reactions of a wide range of (hetero)aryl chlorides, bromides, and triflates with polyfluorophenyl, 2-furan, 2-thiophene, and 2-pyrroleboronic acids and their analogs proceed at room temp. or 40 °C in short reaction times to give the desired products in excellent yields.
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Abstract
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Figure 1
Figure 1. Examples of β–substituent effects on the (a) TEP and (b) geometry of homoleptic phosphines. (a) χ = ν_CO(A₁) – 2056.1 cm^–1 for Ni(CO)₃(PR₃). (b) From solid-state data for Au(PR₃)Cl.(12)
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Scheme 1
Scheme 1. Synthesis and Properties of PAd₃ (1)
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Figure 2
Figure 2. Yield of 6 from reactions in eq 2. L/Pd = 1 in all cases.
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Scheme 2
Scheme 2. Illustrative Examples of 4 as a General Catalyst for Suzuki–Miyaura Coupling of Chloro(hetero)arenes^a
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Scheme aSee SI for 28 additional examples and full experimental details.
Scheme bYield determined by NMR.
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This article references 39 other publications.
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  Multifunctional Chiral Phosphine Organocatalysts in Catalytic Asymmetric Morita-Baylis-Hillman and Related Reactions
  Wei, Yin; Shi, Min
  Accounts of Chemical Research (2010), 43 (7), 1005-1018CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  A review. Catalytic asym. synthesis has received considerable attention over the past few decades, becoming a highly dynamic area of chem. research with significant contributions to the field of org. synthesis. In the development of new catalysts, the concept of multifunctional catalysis described by Shibasaki and co-workers, namely, the combination of more than one functional group within a single mol. to activate the transformation, has proved a powerful strategy in the design of efficient transition metal-contg. catalysts. A variety of reactions have since been addressed with multifunctional organocatalysts. One example is the Morita-Baylis-Hillman (MBH) reaction, in which a carbon-carbon bond is created between the α-position of an activated double-bond compd. and a carbon electrophile. The seminal report on this reaction in 1972 described the prototypical couplings of (i) Et acrylate with acetaldehyde and (ii) acrylonitrile with acetaldehyde; the reaction is promoted by the conjugate addn. of a nucleophilic catalyst to the α,β-unsatd. aldehyde. Many variations of the MBH reaction have been reported, such as the aza-MBH reaction, in which an N-tosyl imine stands in for acetaldehyde. Recent innovations include the development of chiral mols. that catalyze the prodn. of asym. products. In this Account, we describe the refinement of catalysts for the MBH and related reactions, highlighting a series of multifunctional chiral phosphines that we have developed and synthesized over the past decade. We also review similar catalysts developed by other groups. These multifunctional chiral phosphines, which contain Lewis basic and Bronsted acidic sites within one mol., provide good-to-excellent reactivities and stereoselectivities in the asym. aza-MBH reaction, the MBH reaction, and other related reactions. We demonstrate that the reactivities and enantioselectivities of these multifunctional chiral phosphines can be adjusted by enhancing the reactive center's nucleophilicity, which can be finely tuned by varying nearby hydrogen-bonding donors. Artificial catalysts now provide highly economic access to many desirable compds., but the general adaptability and reactivity of these platforms remain problematic, particularly in comparison to nature's catalysts, enzymes. The multifunctional organocatalysts described in this Account represent another pos. step in the synthetic chemist's efforts to profitably mimic nature's catalytic platform, helping develop small-mol. catalysts with enzyme-like reactivities and selectivities.
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  2b
  Reactions of Electron-Deficient Alkynes and Allenes under Phosphine Catalysis
  Lu, Xiyan; Zhang, Chunming; Xu, Zhenrong
  Accounts of Chemical Research (2001), 34 (7), 535-544CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  The development of some new synthetic reactions derived from nucleophilic addn. of phosphines to electron-deficient carbon-carbon triple bonds is reviewed with 40 refs. These reactions show that the phosphine plays the role of a nucleophile as well as an excellent leaving group. The central problem is to generate a 1,3-dipole from alkynoates or allenoates (2,3-butadienoates) by interaction with various phosphines. This study illuminates the unusual phenomena and shows how this understanding allows control of the reaction.
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3. 3
  Sletten, E. M.; Bertozzi, C. R. Acc. Chem. Res. 2011, 44, 666 DOI: 10.1021/ar200148z
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  From Mechanism to Mouse: A Tale of Two Bioorthogonal Reactions
  Sletten, Ellen M.; Bertozzi, Carolyn R.
  Accounts of Chemical Research (2011), 44 (9), 666-676CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  A review. Bioorthogonal reactions are chem. reactions that neither interact with nor interfere with a biol. system. The participating functional groups must be inert to biol. moieties, must selectively reactive with each other under biocompatible conditions, and, for in vivo applications, must be nontoxic to cells and organisms. Addnl., it is helpful if one reactive group is small and therefore minimally perturbing of a biomol. into which it has been introduced either chem. or biosynthetically. Examples from the past decade suggest that a promising strategy for bioorthogonal reaction development begins with an anal. of functional group and reactivity space outside those defined by Nature. Issues such as stability of reactants and products (particularly in water), kinetics, and unwanted side reactivity with biofunctionalities must be addressed, ideally guided by detailed mechanistic studies. Finally, the reaction must be tested in a variety of environments, escalating from aq. media to biomol. solns. to cultured cells and, for the most optimized transformations, to live organisms. Work in our lab. led to the development of two bioorthogonal transformations that exploit the azide as a small, abiotic, and bioinert reaction partner: the Staudinger ligation and strain-promoted azide-alkyne cycloaddn. The Staudinger ligation is based on the classic Staudinger redn. of azides with triarylphosphines first reported in 1919. In the ligation reaction, the intermediate aza-ylide undergoes intramol. reaction with an ester, forming an amide bond faster than aza-ylide hydrolysis would otherwise occur in water. The Staudinger ligation is highly selective and reliably forms its product in environs as demanding as live mice. However, the Staudinger ligation has some liabilities, such as the propensity of phosphine reagents to undergo air oxidn. and the relatively slow kinetics of the reaction. The Staudinger ligation takes advantage of the electrophilicity of the azide; however, the azide can also participate in cycloaddn. reactions. In 1961, Wittig and Krebs noted that the strained, cyclic alkyne cyclooctyne reacts violently when combined neat with Ph azide, forming a triazole product by 1,3-dipolar cycloaddn. This observation stood in stark contrast to the slow kinetics assocd. with 1,3-dipolar cycloaddn. of azides with unstrained, linear alkynes, the conventional Huisgen process. Notably, the reaction of azides with terminal alkynes can be accelerated dramatically by copper catalysis (this highly popular Cu-catalyzed azide-alkyne cycloaddn. (CuAAC) is a quintessential "click" reaction). However, the copper catalysts are too cytotoxic for long-term exposure with live cells or organisms. Thus, for applications of bioorthogonal chem. in living systems, we built upon Wittig and Krebs' observation with the design of cyclooctyne reagents that react rapidly and selectively with biomol.-assocd. azides. This strain-promoted azide-alkyne cycloaddn. is often referred to as "Cu-free click chem.". Mechanistic and theor. studies inspired the design of a series of cyclooctyne compds. bearing fluorine substituents, fused rings, and judiciously situated heteroatoms, with the goals of optimizing azide cycloaddn. kinetics, stability, soly., and pharmacokinetic properties. Cyclooctyne reagents have now been used for labeling azide-modified biomols. on cultured cells and in live Caenorhabditis elegans, zebrafish, and mice. As this special issue testifies, the field of bioorthogonal chem. is firmly established as a challenging frontier of reaction methodol. and an important new instrument for biol. discovery. The above reactions, as well as several newcomers with bioorthogonal attributes, have enabled the high-precision chem. modification of biomols. in vitro, as well as real-time visualization of mols. and processes in cells and live organisms. The consequence is an impressive body of new knowledge and technol., amassed using a relatively small bioorthogonal reaction compendium. Expansion of this toolkit, an effort that is already well underway, is an important objective for chemists and biologists alike.
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4. 4
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  Phosphines: nucleophilic organic catalysts for the controlled ring-opening polymerization of lactides
  Myers, Matthew; Connor, Eric F.; Glauser, Thierry; Mock, Andreas; Nyce, Gregory; Hedrick, James L.
  Journal of Polymer Science, Part A: Polymer Chemistry (2002), 40 (7), 844-851CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)
  A new metal-free synthetic approach to the controlled ring-opening polymn. (ROP) of lactide with nucleophilic phosphines as transesterification catalysts is described. P(Bu)3, PhPMe2, Ph2PMe, PPh3, and related phosphines are com. available, inexpensive catalysts that generate narrowly dispersed polylactides with predictable mol. wts. These org. catalysts must be used in combination with an initiator, such as an alc., to generate an alcoholate ester α-end group upon ROP. A likely polymn. pathway is through a monomer-activated mechanism, with minimal active species, facilitating narrow mol. wt. distributions.
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  Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
  Stephan, Douglas W.; Erker, Gerhard
  Angewandte Chemie, International Edition (2010), 49 (1), 46-76CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  A review. Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form classical Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically frustrated Lewis pairs (FLPs) is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramol. combinations of bulky phosphines or amines with strongly electrophilic RB(C6F5)2 components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H+/H- pairs (stabilized for example, as the resp. phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small mols., including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chem.
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  Main Group Redox Catalysis: Reversible PIII/PV Redox Cycling at a Phosphorus Platform
  Dunn, Nicole L.; Ha, Minji; Radosevich, Alexander T.
  Journal of the American Chemical Society (2012), 134 (28), 11330-11333CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  A planar, trivalent phosphorus compd. is shown to undergo reversible two-electron redox cycling (PIII/PV) enabling its use as catalyst for a transfer hydrogenation reaction. The trivalent phosphorus compd. activates ammonia-borane to furnish a 10-P-5 dihydridophosphorane, which in turn is shown to transfer hydrogen cleanly to azobenzene, yielding diphenylhydrazine and regenerating the initial trivalent phosphorus species. This result constitutes a rare example of two-electron redox catalysis at a main group compd. and suggests broader potential for this nonmetal platform to support bond-modifying redox catalysis dominated by transition metal catalysts.
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9. 9
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  Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis
  Tolman, Chadwick A.
  Chemical Reviews (Washington, DC, United States) (1977), 77 (3), 313-48CODEN: CHREAY; ISSN:0009-2665.
  A review, with 298 refs.
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  Bartik, T.; Himmler, T.; Schulte, H. G.; Seevogel, K.
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  According to Tolman, the χ values of P ligands can be detd. exactly by Fourier transform IR spectroscopy (FTχ values). By replacing the Ph groups of PPh3 by alkyl or alkoxy substituents, giving 157 P ligands, it was found that Tolman's additivity rule is not strictly valid. The deviations from the additivity rule were controlled by the donor-acceptor properties of the atoms bonded to P. Thus, substituents with nearly the same FTΧi parameters, such as OMe vs. SPh or CMe3 vs. SiMe3, but different influences on reactivity (activation vs. inhibition) can be recognized.
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  Wagner, J. P.; Schreiner, P. R. Angew. Chem., Int. Ed. 2015, 54, 12274 DOI: 10.1002/anie.201503476
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  London Dispersion in Molecular Chemistry-Reconsidering Steric Effects
  Wagner, J. Philipp; Schreiner, Peter R.
  Angewandte Chemie, International Edition (2015), 54 (42), 12274-12296CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  A review. London dispersion, which constitutes the attractive part of the famous van der Waals potential, has long been underappreciated in mol. chem. as an important element of structural stability, and thus affects chem. reactivity and catalysis. This negligence is due to the common notion that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly and can amt. to tens of kcal mol-1. This Review collects and emphasizes the importance of inter- and intramol. dispersion for mols. consisting mostly of first row atoms. The synergy of expt. and theory has now reached a stage where dispersion effects can be examd. in fine detail. This forces us to reconsider our perception of steric hindrance and stereoelectronic effects. The quantitation of dispersion energy donors will improve our ability to design sophisticated mol. structures and much better catalysts.
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  Crystal structures of chloro(trimethylphosphine)gold(I), chloro(triisopropylphosphine)gold(I) and bis(trimethylphosphine)gold(I) chloride
  Angermaier, Klaus; Zeller, Edgar; Schmidbaur, Hubert
  Journal of Organometallic Chemistry (1994), 472 (1-2), 371-6CODEN: JORCAI; ISSN:0022-328X.
  The crystal structures of chloro(trimethylphosphine)gold(I) (I), chloro(triisopropylphosphine)gold(I) (II), and bis(trimethylphosphine)gold(I) chloride·2CHCl3 (III) were detd. by single crystal x-ray diffraction studies. At. coordinates are given. I is triclinic, space group P‾1; II is orthorhombic, space group Pna21; and III is tetragonal, space group P‾4. The monomeric units of the mol. complexes I and II have linear P-Au-Cl axes. However, the monomers of I are aggregated to form a helical chain through fairly short alternating Au...Au contacts of 327.1(1), 335.6(1), and 338.6(1) pm and Au-Au-Au angles of 141.6(1), 141.8(1) and 141.9(1)°. By contrast, the monomers of II show no such Au...Au contacts in the lattice. This distinction between the 2 structures of the 2 analogous species is attributed to the different steric requirements of the phosphines. The crystals of III consist of layers of (Me3P)2AuCl complexes sepd. by layers of solvent mols. The P-Au-P coordination is almost linear, with a Cl atom at right angles (Au-Cl 316.7(1) pm, Cl-Au-P 92.3(1)°).
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  Dichlorophosphonites and chlorophosphinates containing an adamantane fragment
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  Reaction of adamantane or 1,3-dimethyladamantane with PCl3 in the presence of AlCl3 gave 94-95% R2P(O)Cl (I; R = adamantyl, 3,5-dimethyl-1-adamantyl).. Redn. of I (R = adamantyl) (II) with LiAlH4 gave 62% R2PH, which upon air oxidn. gave 90% R2P(O)H. Treating II with Br2 and AlBr3 gave 81% I (R = 3-bromo-1-adamantyl).
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  Di-1-adamantylphosphine [(1-Ad)2PH] 1 was synthesized by redn. of (1-Ad)2P(O)Cl with LiAlH4 or HSiCl3. The reaction of 1 with H2O2, elemental sulfur and selenium afforded the corresponding secondary phosphine oxides, sulfides and selenides, (1-Ad)2P(X)H (X = O, S, Se). In the reaction of 1 with two equiv of Me3SiN3 oxidn. occurred with formation of (1-Ad)2P(:NSiMe3)NHSiMe3 6. Despite the steric hindrance, MeI quaternized the P-atom in 1 to give [(1-Ad)2PHMe]I 7. The phosphine (1-Ad)2PMe 8 was formed in the reaction of 7 with NEt3 and was oxidized by O2 to give (1-Ad)2P(O)Me 9.
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  A new method of evaluating the Tolman cone angle from x-ray structural data available from the Cambridge Crystallog. Data Base was developed and a statistical anal. of the cone angles of the phosphines PPh3, PMe2Ph, PMePh2, PMe3, PEt3 and PCy3 (Cy = cyclohexyl) in transition metal complexes was completed.
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  Clavier, Herve; Nolan, Steven P.
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  A New Palladium Precatalyst Allows for the Fast Suzuki-Miyaura Coupling Reactions of Unstable Polyfluorophenyl and 2-Heteroaryl Boronic Acids
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  Boronic acids which quickly deboronate under basic conditions, such as polyfluorophenylboronic acid and five-membered 2-heteroarom. boronic acids, are esp. challenging coupling partners for Suzuki-Miyaura reactions. Nevertheless, being able to use these substrates is highly desirable for a no. of applications. Having found that monodentate biarylphosphine ligands can promote these coupling processes, we developed a precatalyst that forms the catalytically active species under conditions where boronic acid decompn. is slow. With this precatalyst, Suzuki-Miyaura reactions of a wide range of (hetero)aryl chlorides, bromides, and triflates with polyfluorophenyl, 2-furan, 2-thiophene, and 2-pyrroleboronic acids and their analogs proceed at room temp. or 40 °C in short reaction times to give the desired products in excellent yields.
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Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds

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Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds

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