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Updated: May 7, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Rh-catalyzed aldehyde-aldehyde cross-aldol reaction under base-free conditions: in situ aldehyde-derived enolate
Luqing Lin1, Kumiko Yamamoto, Shigeki Matsunaga
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan), Fax: (+81) 3-5684-5206; Kanai Life Science Catalysis Project, ERATO, Japan Science and Technology Agency, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan).
Abstract:
The chemoselective generation of aldehyde-derived enolates to realize an aldehyde-aldehyde cross-aldol reaction is described. A combined Rh/dippf system efficiently promoted the isomerization/aldol sequence by using primary allylic, homoallylic, and bishomoallylic alcohols; secondary allylic and homoallylic alcohols; and trialkoxyboranes that were derived from primary allylic and homoallylic alcohols. The reaction proceeded at ambient temperature under base-free conditions, thus giving cross-aldol products with high chemoselectivity. Mechanistic studies, as well as its application to double-aldol processes under protecting-group-free conditions, are also described.
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