Silylboranes as New Tools in Organic Synthesis
Silylboranes as New Tools in Organic Synthesis
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DOI：
10.1246/bcsj.82.29
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发表时间：
2009-01-15
影响因子：
4
通讯作者：
Suginome, Michinori
中科院分区：
文献类型：
--
作者：
Ohmura, Toshimichi;Suginome, Michinori
介绍了硅基硼烷的新反应性及其在有机合成中的应用。甲硅烷基硼烷在镍、钯和铂催化剂的存在下加成到不饱和有机化合物如炔烃、烯烃、1，3-二烯和联烯上。与异氰化物的反应在没有催化剂的情况下进行，得到1，1-加成产物。硅硼化以高度区域选择性和立体选择性的方式进行，导致形成带有甲硅烷基和硼基的有机化合物。在亚甲基环丙烷和乙烯基环丙烷衍生物的反应中，硅硼化反应伴随着三元环中C-C键的区域选择性断裂。不饱和有机分子，例如，在一个实施例中，1.3-二烯和醛在过渡金属催化剂存在下进行硅硼化C-C偶联反应。实现了末端联烯的对映选择性硅硼化反应和内消旋亚甲基环丙烷的硅硼化C-C断裂。其中立体化学过程，即，顺式和反式立体选择性由配体控制，已经在烯烃的铂催化的分子内硅硼化反应中建立。通过Suzuki-Miyaura偶联、一碳同系、氧化、烯丙基化等方法合成了硅烷化产物。和Rh催化的共轭加成。总结了甲硅烷基硼烷的合成，包括在硅原子上具有杂原子官能团的那些。
New reactivities of silylboranes are described with their applications to organic synthesis. The silylboranes add to unsaturated organic compounds such as alkynes, alkenes, 1,3-dienes, and allenes in the presence of nickel, palladium, and platinum catalysts. Reactions with isocyanide proceed in the absence of catalysts, giving 1,1-addition products. The silaborations proceed in highly regio- and stereoselective manners, leading to the formation of organic compounds bearing silyl and boryl groups. Silaborations accompanied by regioselective C-C bond cleavage in three-membered rings take place in the reactions of methylenecyclopropane and vinylcyclopropane derivatives. Unsaturated organic molecules., e.g., 1.3-diene and aldehyde, undergo silaborative C-C Coupling reactions in the presence of transition-metal catalysts. Enantioselective silaboration of terminal allenes and silaborative C-C cleavage of mesl-methylenecyclopropanes have been achieved. Silaborations in which the stereochemical course, i.e., cis and trans stereoselectivities, is governed by the ligand have been established in platinum-catalyzed intramolecular silaborations of alkenes. Synthetic applications of the silaboration products through Suzuki-Miyaura coupling, one-carbon homologation, oxidation, allylation. and Rh-catalyzed Conjugate addition are also described. Synthesis of silylboranes, including those having heteroatom functional groups at the silicon atoms, is summarized.