Premium
Rh‐Catalyzed AldehydeAldehyde Cross‐Aldol Reaction under Base‐Free Conditions: In Situ Aldehyde‐Derived Enolate Formation through Orthogonal Activation
Author(s) -
Lin Luqing,
Yamamoto Kumiko,
Matsunaga Shigeki,
Kanai Motomu
Publication year - 2013
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201300928
Subject(s) - aldehyde , aldol reaction , allylic rearrangement , chemoselectivity , chemistry , isomerization , catalysis , organic chemistry , protecting group , alkyl
The chemoselective generation of aldehyde‐derived enolates to realize an aldehydealdehyde 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.