P[N(i-Bu)CH2CH2]3N: Nonionic Lewis Base for Promoting the Room-Temperature Synthesis of α,β-Unsaturated Esters, Fluorides, Ketones, and Nitriles Using

详细信息    查看全文

• 作者：Venkat Reddy Chintareddy ; Arkady Ellern ; John G. Verkade
• 刊名：Journal of Organic Chemistry
• 出版年：2010
• 出版时间：November 5, 2010
• 年：2010
• 卷：75
• 期：21
• 页码：7166-7174
• 全文大小：1053K
• 年卷期：v.75,no.21(November 5, 2010)
• ISSN：1520-6904

文摘

The bicyclic triaminophosphine P(RNCH₂CH₂)₃N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth−Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.