Abstract

Catalytic asymmetric formal total syntheses of both antipodes of sesquiterpene, (+)‐ar‐macrocarpene (1) and (–)‐ar‐macrocarpene (ent‐1) has been achieved from 5,5‐dimethyl‐(3‐p‐tolyl)cyclohexanone 12. Enantioenriched compound 12 was obtained in excellent yield with 96 % ee by catalytic enantioselective p‐tolylboronic acid addition to 5,5‐dimethyl cyclohexen‐2‐one 13 using Rh(I)‐(S)‐BINAP (L7). Moreover, ent‐12 was achieved in 96 % ee by using Rh(I)‐(R)‐BINAP (ent‐L7).

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