Premium
Cascade Triple‐Aldehyde Addition of 1,2,3,4‐Tetrakis(pinacolatoboryl)but‐ 2‐ene: Stereoselective Synthesis of 2,3‐Bis(alkylidene)alkane‐1,5‐diols
Author(s) -
Shimizu Masaki,
Shimono Katsuhiro,
Hiyama Tamejiro
Publication year - 2007
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.200700153
Subject(s) - aldehyde , chemistry , alkane , stereoselectivity , ene reaction , toluene , organic chemistry , medicinal chemistry , catalysis
Treatment of ( Z )‐1,2,3,4‐tetrakis(pinacolatoboryl)but‐2‐ene, prepared from 2,3‐bis(pinacolatoboryl)buta‐1,3‐diene and bis(pinacolato)diboron, with three molar equivalents of aldehyde in toluene at 100 °C gave the 2,3‐bis(alkylidene)alkane‐1,5‐ anti ‐diol as a single stereoisomer. The reaction is applicable to both aromatic and α‐unbranched aliphatic aldehydes. The 1,5‐ anti ‐diols were also synthesized by the one‐pot preparation/triple‐aldehyde addition of the tetraborylated butene. Experimental results for the stepwise treatment of the butene with two types of aldehydes suggest that the rate‐determining step of the triple‐aldehyde addition is the third allylation.