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Palladium‐Catalyzed Umpolung Type‐II Cyclization of Allylic Carbonate‐Aldehydes Leading to 3‐Methylenecycloalkanol Derivatives
Author(s) -
Tsukamoto Hirokazu,
Kawase Ayumu,
Doi Takayuki
Publication year - 2019
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201900450
Subject(s) - chemistry , umpolung , palladium , allylic rearrangement , aldehyde , medicinal chemistry , catalysis , formate , organic chemistry , ligand (biochemistry) , combinatorial chemistry , nucleophile , biochemistry , receptor
Palladium‐catalyzed umpolung type‐II cyclization of allylic carbonate‐aldehydes leading to 3‐methylenecycloalkanol derivatives was developed. The formate reductant was effective for the cyclization without causing a reduction of the η 3 ‐allylpalladium intermediate. One‐pot decarboxylative allylation of aldehyde‐containing malonate with 2‐[(acetyloxy)methyl]‐2‐propenyl methyl carbonate followed by the cyclization of the allyl acetate‐aldehyde formed in situ was also achieved. The high diastereoselectivities observed in the cyclization of branched substrates indicates that a chair‐chair transition state should be involved. Based on the presumed transition state, we could predict the enantioselectivity of the cyclization using SEGPHOS as a chiral diphosphine ligand and obtain optically active alcohols in up to 95:5 er .