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Asymmetric Diels ‐ Alder Reactions of Neopentyl‐Ether‐Shielded Acrylates and Allenic Esters: Syntheses of (−)‐Norbornenone and (−)‐β‐Santalene
Author(s) -
Oppolzer Wolfgang,
Chapuis Christian,
Dupuis Dominique,
Guo Maodao
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680803
Subject(s) - chemistry , cyclopentadiene , enantioselective synthesis , adduct , cycloaddition , methyl acrylate , organic chemistry , diels–alder reaction , ether , camphor , medicinal chemistry , catalysis , copolymer , polymer
Starting from (+)‐ or (−)‐camphor, the antipodal alcohols 14 and 18 , respectively, have been prepared; the corresponding acrylates 15 and 19 underwent TiCl 2 (i‐PrO) 2 ‐mediated Diels ‐ Alder additions to cyclopentadiene to give adducts 20a and 22a respectively, with 95 % endo ‐ and 99.2% πpH‐face selectivities. Adduct 22a was converted to enantiomerically pure norbornenone 26 . Addition of 1,3‐butadiene to acrylate 15 in the presence of TiCl 4 afforded 3‐cyclohexenyl carboxylate 29 with > 95.6 % stereodifferentiation. The TiCl 2 (i‐PrO) 2 ‐promoted [4 + 2] cycloaddition of cyclopentadiene to allenic ester 43 proceeding with 99 % face differentiation served as the key step for an efficient enantioselective synthesis of (−)‐β‐santalene ((−)‐ 41 ) with concomitant recovery of the chiral control alcohol 14 .