Mechanism of Metal-Free C鈥揌 Activation of Branched Aldehydes and Acylation of Alkenes Using Hypervalent Iodine Compound: A Theoretical Study

详细信息    查看全文

• 作者：Julong Jiang ; Romain Ramozzi ; Shin Moteki ; Asuka Usui ; Keiji Maruoka ; Keiji Morokuma
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：September 18, 2015
• 年：2015
• 卷：80
• 期：18
• 页码：9264-9271
• 全文大小：540K
• ISSN：1520-6904

文摘

The mechanism of the C鈥揌 activation of aldehydes and the succeeding acylation of an alkene using a hypervalent iodine reagent is investigated by theoretical calculations. In contrast to the initial proposed mechanism, the present calculations show that the hypervalent iodine is the initiator of the radical reaction. The formation of acyl radical is rate-determining, and the resulting radical acts as the chain carrier. The kinetic isotope effect (KIE) of deuterated aldehyde, as well as other experimental observations, can now be rationalized from the newly proposed mechanism.