Asymmetric <i>Diels</i>‐<i>Alder</i> Reactions of Neopentyl‐Ether‐Shielded Acrylates and Allenic Esters: Syntheses of (−)‐Norbornenone and (−)‐β‐Santalene

Abstract

Abstract 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 &gt; 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 .