Dual role of silanol groups in cyclopropanation and Hiyama-Denmark cross-coupling reactions.
Di-tert-butoxy(alkenyl)silanols serve as substrates in the Simmons-Smith cyclopropanation reaction furnishing the corresponding di-tert-butoxy(cyclopropyl)silanols, which may be included in a Hiyama-Denmark cross-coupling reaction. The silanol group bears two distinct roles as it provides a directing group during the cyclopropanation and mediates the transmetalation event in the cross-coupling. The nature of the ligands on the silicon atom had a profound effect on reactivity in the cross-coupling, whereby substituting the alkoxide groups for fluorides allowed for efficient cross-coupling.
Beaulieu
Louis-Philippe B
LP
Département de Chimie, Université de Montreal, P.O. Box. 6138, Station Downtown Montréal, Québec, Canada H3C 3J7.
Delvos
Lukas B
LB
Charette
André B
AB
D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D012821:Silanes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
D003521:Cyclopropanes; D012821:Silanes; C082343:silanol