135987-50-7Relevant articles and documents
Palladium/Me3SiOTf-catalyzed bis-silylation of α,β-unsaturated carbonyl compounds without involving oxidative addition of disilane
Ogoshi, Sensuke,Tomiyasu, Sadayuki,Morita, Masaki,Kurosawa, Hideo
, p. 11598 - 11599 (2002)
In the presence of a catalytic amount of Me3SiOTf and palladium(0), the addition of disilane to α,β-unsaturated carbonyl compounds proceeds under very mild conditions via η3-siloxyallylpalladium generated by the reaction of enone, en
Catalytic Reductive Cross-Coupling between Aromatic Aldehydes and Arylnitriles
Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
, p. 7094 - 7098 (2021)
A reductive cross-coupling reaction between aromatic aldehydes and arylnitriles using a copper catalyst and a silylboronate as a reductant is reported. This protocol represents an unprecedented approach to the chemoselective synthesis of α-hydroxy ketones by electrophile–electrophile cross-coupling.
Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations
Deng, Yifan,Liu, Qi,Smith, Amos B.
supporting information, p. 9487 - 9490 (2017/07/24)
Oxidative [1,2]-Brook rearrangements via hypervalent silicon intermediates induced by photoredox-catalyzed single-electron transfer have been achieved, permitting the formation of reactive radical species that can engage in alkylations and arylations.
Carboxylation with CO2 via brook rearrangement: Preparation of α-hydroxy acid derivatives
Mita, Tsuyoshi,Higuchi, Yuki,Sato, Yoshihiro
supporting information, p. 14 - 17 (2014/01/23)
In the presence of CsF, a wide range of α-substituted α-siloxy silanes were carboxylated under a CO2 atmosphere (1 atm) via Brook rearrangement. A variety of α-substituents including aryl, alkenyl, and alkyl groups were tolerated to afford α-hydroxy acids in moderate-to-high yields. One-pot synthesis from aldehydes using PhMe2SiLi and CO 2 was also possible, providing α-hydroxy acids without the isolation of an α-hydroxy silane.
Copper-catalyzed addition of nucleophilic silicon to aldehydes
Cirriez, Virginie,Rasson, Corentin,Hermant, Thomas,Petrignet, Julien,Diaz Alvarez, Jesus,Robeyns, Koen,Riant, Olivier
supporting information, p. 1785 - 1788 (2013/04/10)
How to train your silane: A new family of chiral copper(I) complexes that bear a bifluoride counteranion were prepared and used in the first example of the enantioselective transfer of a silyl group to an aldehyde. This procedure provides fast access to non-racemic α-hydroxysilanes in high enantioselectivities. Copyright
Copper-catalyzed 1,2-addition of nucleophilic silicon to aldehydes: Mechanistic insight and catalytic systems
Kleeberg, Christian,Feldmann, Evgenia,Hartmann, Eduard,Vyas, Devendra J.,Oestreich, Martin
supporting information; experimental part, p. 13538 - 13543 (2012/01/06)
Activation of the Si-B inter-element bond with copper(I) alkoxides produces copper-based silicon nucleophiles that react readily with aldehydes to yield α-silyl alcohols (that is, α-hydroxysilanes) after hydrolysis. Two independent protocols were develope
Metal-free catalytic C-Si bond formation in an aqueous medium. enantioselective NHC-catalyzed silyl conjugate additions to cyclic and acyclic α,β-unsaturated carbonyls
O'Brien, Jeannette M.,Hoveyda, Amir H.
body text, p. 7712 - 7715 (2011/07/09)
A metal-free method for enantioselective conjugate addition of a dimethylphenylsilyl group to α,β-unsaturated carbonyls is reported. Transformations are catalyzed by a chiral N-heterocyclic carbene (NHC), performed in an aqueous solution (3:1 mixture of water and tetrahydrofuran) and are operationally simpler to perform than the NHC-Cu-catalyzed variant. The chiral catalyst is generated from an enantiomerically pure imidazolinium salt (prepared in three steps) and a common organic amine base (dbu). NHC-catalyzed processes proceed with 5.0-12.5 mol % catalyst loading at 22 °C within 1-12 h, affording the desired β-silyl carbonyls in 85:15 to >98:2 enantiomeric ratio and in 50% to >98% yield. Cyclic enones or lactones and acyclic α,β-unsaturated ketones, esters, and aldehydes can be used as substrates.
Metal-free relay oxidation: Valuable synthesis of acylsilane and ketones under aerobic oxidation
Bai, Xing-Feng,Gao, Guang,Zheng, Zhan-Jiang,Li, Fei,Lai, Guo-Qiao,Jiang, Kezhi,Li, Fuwei,Xu, Li-Wen
, p. 3031 - 3035 (2012/01/05)
In this letter, an example of interesting metal-free relay air oxidation of -hydroxysilanes, promoted by the hydroperoxidated carbonyl compounds derived from the Michael reaction of 5,5-dimethylcyclohexane-1,3-dione and chalcone, is reported. A series of aromatic acylsilanes with TBDPS were obtained in promising isolated yields. In addition, as an extension of the relay oxidation under aerobic conditions, this catalyst-free relay oxidation induced by diketone can be applied to the oxidation of general aromatic alcohols (up to 75% yield). Georg Thieme Verlag Stuttgart · New York.
Enzymatic kinetic resolution of α-hydroxysilanes
An, Ilhwan,Onyeozili, Edith N.,Maleczka Jr., Robert E.
experimental part, p. 527 - 534 (2010/08/22)
The enzymatic kinetic resolution of α-hydroxysilanes where the silicon bears a variety of substituents has been explored. Reactions were performed on various α-hydroxysilanes with several commercially available enzymes, solvents, acetylation reagents, and temperatures. The resulting optically active α-hydroxysilanes and their corresponding acetates were obtained in varying yields and ees.
Synthesis of Optically Pure Arylsilylcarbinols and Their Use as Chiral Auxiliaries in Oxacarbenium Ion Reactions
Huckins, John R.,Rychnovsky, Scott D.
, p. 10135 - 10145 (2007/10/03)
A family of arylsilylcarbinols was synthesized and investigated as chiral auxiliaries for oxacarbenium ion reactions. The optically pure arylsilylcarbinols were prepared using Noyori's transfer hydrogenation catalyst 11. The transfer hydrogenation shows very good enantioselectivities and turnover efficiency for the aryl silyl ketones and is the method of choice for preparing these optically pure alcohols. The diastereoselective addition of allyltrimethylsilane to an in situ generated oxacarbenium ion was explored using Marko's conditions. The selectivity for a representative aliphatic aldehyde was very good, but the selectivity was significantly reduced with unsaturated and aromatic aldehydes. The range of selectivities with different auxiliaries was narrow, and the most practical auxiliary is the phenylsilylcarbinol 2.
