Synthesis of Verbenindenes: A New Class of Chiral Indenyl Ligands Derived from Verbenone

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• 作者：Kenneth C. Rupert ; Charles Chao Liu ; Tam T. Nguyen ; Mark A. Whitener ; and John R. Sowa Jr.
• 刊名：Organometallics
• 出版年：2002
• 出版时间：January 7, 2002
• 年：2002
• 卷：21
• 期：1
• 页码：144 - 149
• 全文大小：96K
• 年卷期：v.21,no.1(January 7, 2002)
• ISSN：1520-6041

文摘

A new class of chiral indenes (verbenindenes), in which a verbenone moiety is annulatedto an indene core, is prepared by a sequence of Shapiro lithiation and Nazarov cyclizationreactions. Since the initial indenes are resistant to deprotonation, they are isomerized via[1,5]-sigmatropic shifts to obtain indenes that are readily deprotonated with n-butyllithium.Reaction of the indenide anions with chloro(1,5-cycloctadiene)rhodium dimer producesverbenindenyl transition-metal complexes. Coordination of the indenyl ligand may occurwith the gem-dimethyl bridge of the verbenone moiety syn or anti to the metal. Selectivityfavors the less hindered anti complexes, and a crystal structure of a member of this seriesis presented.