Diphenylsilane
Sandra Forbes
Product Manager
Recent Literature
The utilization of a catalytic quantity of N-heterocyclic carbene (NHC) facilitates the activation of diphenylsilane, enabling the hydrosilylation of carbonyl derivatives to occur under gentle conditions. It is hypothesized that the process involves the formation of a hypervalent silicon intermediate, endowed with pronounced Lewis acid properties, which facilitates dual activation—simultaneously targeting both the carbonyl group and the hydride moiety at the silicon center. This approach has yielded intriguing selectivities in the reaction outcomes.
Q. Zhao, D. P. Curran, M. Malacria, L. Fensterbank, J.-P. Goddard, E. Lacôte, Synlett, 2012, 23, 433-437.
The catalytic system consisting of [RuCl2(p-cymene)]2 and Ph2SiH2 exhibits remarkable efficiency in the reductive amination of aldehydes with anilines, affording secondary and tertiary amines in satisfactory yields. This method boasts high chemoselectivity and exhibits a broad compatibility with diverse functional groups, encompassing NO2, CN, CO2Me, F, Cl, Br, OMe, Me, furyl, and alkyl moieties, underscoring its versatility and practical applicability.
B. Li, J. Zheng, W. Zeng, Y. Li, L. Chen, Synthesis, 2017, 49, 1349-1355.
An eco-friendly and tin-free radical "on water" methodology has been devised for the addition of alkyl iodides to the C=N bond of hydrazones, utilizing diphenylsilane and triethylborane as promoters. This approach efficiently yields the corresponding addition products in good quantities. Notably, the established protocol finds application in the synthesis of 3-substituted isoindolinone derivatives, showcasing its practical value in organic synthesis.
T. K. Nam, D. O. Jang, J. Org. Chem., 2018, 83, 7373-7379.
A highly chemoselective organophosphorus-catalyzed reductive coupling reaction has been developed for the formation of C-N bonds between nitroalkanes and arylboronic acids/esters. This method exhibits exceptional selectivity towards the nitro/boronic acid substrate pair, enabling the efficient synthesis of functionalized N-(hetero)arylamines.
G. Li, Y. Kanda, S. Y. Hong, A. T. Radosevich, J. Am. Chem. Soc., 2022, 144, 8242-8248.
DOI: 10.1021/jacs.2c01487
A combination of Co(OAc)2 and a chiral phosphine-amido-oxazoline (PAO) ligand serves as an effective catalyst for the mild and asymmetric hydrosilylation of α-oxygenated ketones, yielding synthetically valuable 1,2-diol derivatives. These optically enriched products can be further transformed into chiral α-hydroxy acids, 1,3-dioxolan-2-ones, ethylene oxides, and 1,2,3-1H-triazoles, showcasing their versatility in organic synthesis.
H. Wen, Y. Chen, L. Shi, J. Chen, Y. Luo, Y. Xia, Org. Lett., 2023, 25, 2184-2189.
DOI: 10.1021/acs.orglett.3c00162
The employment of axially chiral BINAM N-heterocyclic carbene (NHC)-Rh(III) complexes as catalysts enables a gentle and enantioselective hydrosilylation of 3-oxo-3-arylpropionic acid methyl or ethyl esters. This process efficiently furnishes 3-hydroxy-3-arylpropionic acid methyl or ethyl esters in good yields, accompanied by good to excellent enantioselectivities, all under mild reaction conditions.
Q. Xu, X. Gu, S. Liu, Q. Duo, M. Shi, J. Org. Chem., 2007, 72, 2240-2242.
DOI: 10.1021/jo062453d
A versatile system combining an air-stable Ni precatalyst, dimethyl dicarbonate as an activator, and diphenylsilane as a reductant, facilitates the direct transformation of carboxylic acids into aldehydes across a broad spectrum of substrates. This method achieves good yields without any overreduction to alcohols, demonstrating its effectiveness and precision in aldehyde synthesis.
A. V. Iosub, S. Moravčík, C.-K. Wallentin, J. Berman, Org. Lett., 2019, 21, 7804-7808.
DOI: 10.1021/acs.orglett.9b02779
A phosphine-catalyzed Wittig reaction utilizing 3-methyl-1-phenylphospholane-1-oxide as the precatalyst and an organosilane as the reducing agent serves as the cornerstone for the efficient conversion of diverse heteroaryl, aryl, and alkyl aldehydes into their corresponding alkenes in good yields. This protocol not only demonstrates high efficacy but also scales up seamlessly to larger reactions, underscoring its practical value in organic synthesis.
C. J. O'Brien, J. L. Tellez, Z. S. Nixon, L. J. Kang, A. L. Carter, S. R. Kunkel, K. C. Przeworski, G. A. Chass, Angew. Chem. Int. Ed., 2008, 48, 6836-6839.
A seamless one-pot process integrates Cu-catalyzed asymmetric conjugate reduction of β-substituted ketones, yielding enantiomerically enriched diphenylsilyl enol ethers. These intermediates then undergo a diastereoselective Pd-catalyzed α-arylation with various aryl bromides, resulting in disubstituted cycloalkanones of exceptional enantiomeric and diastereomeric purity. This integrated protocol streamlines the synthesis of highly pure cycloalkanone derivatives.
J. Chae, J. Yun, S. L. Buchwald, Org. Lett., 2004, 6, 4809-4812.
DOI: 10.1021/ol048313c
A catalytic anti-Markovnikov hydrobromination of aryl- and alkyl-substituted terminal alkynes efficiently produces terminal E-alkenyl bromides in high yields, accompanied by exceptional regio- and diastereoselectivity. This methodology boasts compatibility with a broad spectrum of functional groups, encompassing esters, nitriles, epoxides, aryl boronic esters, terminal alkenes, silyl ethers, aryl halides, and alkyl halides, thereby expanding its applicability in organic synthesis.
M. R. Uehling, R. P. Rucker, G. Lalic, J. Am. Chem. Soc., 2014, 136, 8799-8803.
DOI: 10.1021/ja503944n
Cu(I) catalysis facilitates the efficient and straightforward synthesis of trisubstituted exocyclic alkenes under mild conditions, with B2pin2 serving as a crucial additive. This approach yields the desired products in good amounts and can also lead to the isolation of tetrasubstituted borylated or iodinated alkenes, contingent upon the reaction parameters. Preliminary mechanistic investigations reveal that the reaction proceeds via a radical pathway, with B2pin2 playing a pivotal role in the process.
S. Zhou, F. Yuan, M. Guo, G. Wang, X. Tang, W. Zhao, Org. Lett., 2018, 20, 6710-6714.
DOI: 10.1021/acs.orglett.8b02801
A minute phosphacyclic (phosphetane) catalyst orchestrates the synthesis of unsymmetrical hydrazines through a cross-selective intermolecular N-N reductive coupling between nitroarenes and anilines. In this reaction, a hydrosilane functions as the terminal reductant, contributing to a process that displays excellent chemoselectivity and a robust tolerance towards various functional groups.
G. Li, S. P. Miller, A. T. Radosevich, J. Am. Chem. Soc., 2021, 143, 14464-14469.
DOI: 10.1021/jacs.1c07272
Quoted from: https://www.organic-chemistry.org/chemicals/reductions/diphenylsilane.shtm
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