C-Si Bond Formation
Reactions
Hydrosilylation
Electrophilic Silylation
Silaboration
Recent Literature
The silylation of various aryl iodides with 1,1,1,3,5,5,5-heptamethyltrisiloxane
was achieved using transition-metal catalysts, such as Pd(0), Pt(0), and Rh(I),
which offer a dramatically different substrate scope.
M. Murata, K. Ota, H. Yamasaki, S. Watanabe, Y. Masuda, Synlett, 2007,
1387-1390.
High yields were achieved by using [Rh(cod)(MeCN)2]BF4
as catalyst in a specific silylation of aryl iodides and bromides with
triethoxysilane in the presence of NEt3. This new reaction
tolerates different functional groups and therefore often eliminates the
need to use protective groups (compared to previous methods via Grignard
reagents).
M. Murata, M. Ishikura, M. Nagata, S. Watanabe, Y. Masuda, Org. Lett., 2002, 4, 1843-1845.
The nickel-catalyzed reaction of terminal alkenes with silacyclobutanes afforded
the corresponding vinylsilanes in a highly regio- and stereoselective fashion.
The reaction provides a facile access to vinylsilanes starting from trivial
terminal alkenes as well as styrenes, 1,3-dienes, and acrylate esters.
K. Hirano, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc., 2007,
129, 6094-6095.
A new approach to 2-(arylmethyl)aldehydes is presented. The sequence starts
with a silylformylation reaction of terminal acetylenes with aryl- or
heteroarylsilanes, which is followed by a TBAF-induced 1,2-anionotropic
rearrangement.
L. A. Aronica, P. Raffa, A. M. Caporusso, P. Salvadori, J. Org. Chem.,
2003, 5, 9292-9298.
In the presence of cationic rhodium complexes, Si-B compounds function as equivalents of nucleophilic silicon, which is
efficiently transferred onto acyclic as well as cyclic α,β-unsaturated carbonyl
compounds. [((S)-binap)Rh(cod)]ClO4 has effected an asymmetric
1,4-addition to cyclic acceptors in high enantiomeric excess.
C. Walter, G. Auer, M. Oestreich, Angew. Chem. Int. Ed., 2006, 45, 5675-5677.
K.-J. Chang, D. K. Rayabarapu, F.-Y. Yang, C.-H. Cheng, J. Am. Chem. Soc.,
2005,127, 126-131.
A new method for the synthesis of substituted 2-acylallylmetal reagents in a
highly regio- and stereoselective fashion involving a three-component
assembly of allenes, acyl chlorides, and bimetallic reagents (B-B, Si-Si,
and Sn-Sn) catalyzed by phosphine-free palladium complexes is described.
F.-Y. Yang, M. Shanmugasundaram, S.-Y. Chuang, P.-J. Ku, M.-Y. Wu, C.-H.
Cheng, J. Am. Chem. Soc.,
2003, 125, 12576-12583.
Highly efficient, stereo- and regioselective palladium-catalyzed
hydro-, sila-, and stannastannations of cyclopropenes gave multisubstituted
cyclopropylstannanes. The addition across
the double bond proceeds from the least hindered face.
M. Rubina, M. Rubin, V. Gevorgyan, J. Am. Chem. Soc., 2002, 124, 11566-11567.
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