129156-45-2Relevant academic research and scientific papers
Conformational Bias by a Removable Silyl Group: Construction of Bicyclo[n.3.1]alkenes by Ring Closing Metathesis
Lin, Minggui,Cai, Pei-Jun,Zeng, Zhixiong,Lin, Na,Shen, Yang,Tang, Bin,Li, Fan,Chen, Chen,Yu, Zhi-Xiang,Zhang, Yandong
, p. 2334 - 2338 (2018)
Herein, we report a novel strategy based on a conformationally controlled RCM by a removable silyl group, which allows the facile synthesis of various bicyclo[n.3.1]alkenes, especially a set of highly strained bicyclo[5.3.1]alkenes. Further derivatizations of the silyl group and the resultant double bond of bicyclo[5.3.1]undecene 2 f enabled a concise synthesis of A-B-C ring skeleton of taxol. Density functional theory (DFT) calculations suggest that the introduction of a bulky silyl group at C-5 position of the 1,3-dialkenylcyclohexanol substrates dramatically lowers the energy bias gap between diaxial conformers (to RCM) and diequatorial conformers (to cross metathesis), thereby favoring the expected RCM reaction to give the challenging bridged molecules.
Silver(I)-catalyzed ring-contractive rearrangement: A new entry to 5-alkylidene-2-cyclopentenones
Zhao, Liang,Wang, Jinlian,Zheng, Hongyan,Li, Yun,Yang, Ke,Cheng, Bin,Jin, Xiaojie,Yao, Xiaojun,Zhai, Hongbin
supporting information, p. 6378 - 6381 (2015/01/09)
A novel silver(I)-catalyzed ring-contractive rearrangement of 5-substituted 6-diazo-2-cyclohexenones has been developed, providing a new and efficient access to 5-alkylidene-2-cyclopentenones. The AgOTf-catalyzed reaction proceeds through metal-carbenoid formation followed by endocyclic allyl [1,2] migration with excellent stereoselectivity and broad substrate scope.
Diastereoselective 1,4-addition of various nucleophiles to 5-trimethylsilyl-2-cyclohexenone: Synthesis of (+)-ramulosin
Asaoka, Morio,Sonoda, Shuzo,Fujii, Naoaki,Takei, Hisashi
, p. 1541 - 1552 (2007/10/02)
Base catalyzed reaction of active methylene compounds or oxygen catalyzed reaction of trialkylboranes via radical pathway with 5-trimethylsilyl-2-cyclohexenone (1) gave the corresponding products with modest to high (3:2- 20:1) diastereopurities. High dia
