Hexamethylsilirane. 5. Conversion to five-membered ring silicon compounds by two-atom insertion reactions of aryl olefins, 1,3-dienes and conjugated acetylenes

Advances in the Synthesis and Applications of Three Membered Sila, Sila‐Aza/‐Phospha/‐Oxa/‐Thia Cyclopropanes

“…Later, in 1984, Seyferth and his group extended their studies on the double bond insertion process in detail and it is briefed in Scheme 6. [ 16 ] Compounds with conjugated double bond 39 yielded corresponding double bond insertion product 42 in addition to the silylene adduct of diene 43 . The two atom insertion products ( 44–46 ) were also achieved with compounds bearing triple bond, such as phenyl acetylene 40 and benzyne 41 as mentioned in the Scheme 6.…”

“…[ 4–6 ] In addition to the simple nucleophile trigered ring opening of silacyclopropane, Seyferth et al disclosed the novel “two atom” (olefin) insertion into silirane ring to provide silacyclopentane in 1984. [ 16 ] Later, insertion reactions of alkyne, [ 48a ] aldehydes/ketones, [ 48b ] silylenes, [ 49 ] chalcogens, [ 50 ] isocyanides [ 24 ] into siliranes to provide corresponding Si‐containing expanded ring were also developed. Although, reasonable number of research groups were involved in exploring the synthesis and synthetic prospects of silirane, Woerpol and his team did an extensive study to establish its synthetic capabilities.…”

Catalytic Generation of Rhodium Silylenoid for Alkene–Alkyne–Silylene [2 + 2 + 1] Cycloaddition

“…The ring formation took place with release of phenyl or methyl groups through Si−C bond cleavage. Ph− B(pin) (9) and Me−B(pin) (10) were also formed and present in the reaction mixture. Some reports describe the rhodium-catalyzed formation of five-membered silacarbocycles through substitution of the methyl or phenyl groups on silicon, 6e,h,16,17 where an elementary step shown in Scheme 3 is suggested.…”

Development of Reactions of Silacyclopropanes as New Methods for Stereoselective Organic Synthesis

“…We found this situation to be paradoxical considering the unique reactivity of silicon compounds and their important role in organic chemistry. 7,8 Although significant contributions to silacyclopropane chemistry have been reported by Seyferth et al, [9][10][11][12][13] Ando et al, 14 and others, [15][16][17] the reactions of silacyclopropanes have not been extended to organic synthesis.…”