17876-95-8Relevant academic research and scientific papers
N-Heterocyclic carbene-mediated organocatalytic transfer of tin onto aldehydes: New access to α-silyloxyalkylstannanes and γ- silyloxyallylstannanes
Blanc, Romain,Commeiras, Laurent,Parrain, Jean-Luc
, p. 661 - 666 (2010)
A new, highly efficient and mild N-heterocyclic carbene (NHC)-mediated organocatalytic procedure for the transfer of tin from tributyl(trimethylsilyl) stannane (Bu3SnSiMe3) onto aldehydes for the preparation of α-silyloxyalkylstannanes and γ-silyloxyallylstannanes has been developed.
Reactions of silyl-stabilised sulfur ylides with organoboranes: Enantioselectivity, mechanism, and understanding
Howells, Dean,Robiette, Raphael,Fang, Guang Y.,Knowles, Luke S.,Woodrow, Michael D.,Harvey, Jeremy N.,Aggarwal, Varinder K.
, p. 1185 - 1189 (2008)
The reaction of trimethylsilyl-substituted sulfonium ylides with organoboranes (Ph3B, Et3B) has been studied and although homologated products were obtained in good yield (after oxidation to the corresponding alcohols), the enantiomeric excesses were low with our camphor-based chiral sulfide (up to 40% ee, cf. corresponding phenyl-substituted sulfonium ylides gave >95% ee). Cross-over experiments were conducted to ascertain the nature of this difference in selectivity. Thus, aryl- and silyl-substituted sulfonium ylides (1 equiv.) were (separately) reacted with Et3B (1.5 equiv.) followed by Ph3B (1.5 equiv.) The experiments were repeated changing the order of addition of the two boranes. It was found that the aryl-substituted sulfonium ylide only trapped the first borane that was added indicating that ate complex formation was non-reversible and so was the selectivity determining step. In contrast the silyl-substituted sulfonium ylide only trapped Ph3B (it is more reactive than Et 3B) indicating that ate complex formation was reversible and so 1,2-migration was now the selectivity determining step. The reactions have been studied computationally and the experimental observations have been reproduced. They have further revealed that the cause of reversibility in the case of the silyl-substituted sulfonium ylides results from ate complex formation being less exothermic and a higher barrier to 1,2-migration. This journal is The Royal Society of Chemistry.
Controllable one-pot synthesis for scaffold diversity: Via visible-light photoredox-catalyzed Giese reaction and further transformation
Nam, Su Been,Khatun, Nilufa,Kang, Young Woo,Park, Boyoung Y.,Woo, Sang Kook
, p. 2873 - 2876 (2020/03/19)
This study presents a controllable one-pot synthesis for constructing valuable scaffolds (alcohols, 2,3-dihydrofurans, α-cyano-γ-butyrolactones, and γ-butyrolactones) via a visible-light photoredox-catalyzed Giese reaction and further transformation. This
Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling
Hofstra, Julie L.,Cherney, Alan H.,Ordner, Ciara M.,Reisman, Sarah E.
supporting information, p. 139 - 142 (2018/01/17)
An asymmetric Ni-catalyzed reductive cross-coupling has been developed to prepare enantioenriched allylic silanes. This enantioselective reductive alkenylation proceeds under mild conditions and exhibits good functional group tolerance. The chiral allylic silanes prepared here undergo a variety of stereospecific transformations, including intramolecular Hosomi-Sakurai reactions, to set vicinal stereogenic centers with excellent transfer of chirality.
Visible-Light Photoredox-Catalyzed Hydroalkoxymethylation of Activated Alkenes Using α-Silyl Ethers as Alkoxymethyl Radical Equivalents
Khatun, Nilufa,Kim, Myeong Jun,Woo, Sang Kook
, p. 6239 - 6243 (2018/09/27)
A new neutral silicon-based traceless activation group (TAG) for visible-light photoredox-catalyzed hydroalkoxymethylation of alkenes is presented. This reaction involves in-situ-generated alkoxymethyl radical via single electron oxidation (SET) of α-TMS-substituted ethers, followed by subsequent conjugate addition to activated alkenes. Various functional groups were tolerated both under mild metal and metal-free conditions to provide good to excellent yields. Furthermore, the addition products were transformed to valuable synthetic building blocks, such as carboxylic acids,-butyrolactones, and complex aryl alkyl ethers.
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.
A Lewis acid-promoted reduction of acylsilanes to α-hydroxysilanes by diethylzinc
Gao, Guang,Bai, Xing-Feng,Li, Fei,Zheng, Long-Sheng,Zheng, Zhan-Jiang,Lai, Guo-Qiao,Jiang, Kezhi,Li, Fuwei,Xu, Li-Wen
supporting information; experimental part, p. 2164 - 2166 (2012/05/05)
We report here the first example of the reduction of acylsilanes to α-hydroxysilanes, in which diethylzinc was used as a highly reactive agent in the presence of Ti(OiPr)4 or other Lewis acids. The reduction typically proceeds to give synthetically useful α-hydroxysilanes in good yields.
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
supporting information; experimental part, 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 and fluoride-promoted Wittig rearrangements of α-alkoxysilanes
Maleczka Jr., Robert E.,Geng, Feng
, p. 1111 - 1113 (2008/02/09)
(matrix presented) Lewis acid-catalyzed reaction of allyl and benzyl trichloroacetimidates with α-silyl alcohols was found to be a general method for the synthesis of α-alkoxysilanes. Upon exposure to CsF, these α-alkoxysilanes could be made to undergo [2,3]-Wittig rearrangement with an efficiency similar to that realized by the analogous but inherently more toxic α-alkoxystannanes.
