Novel Wagner-Meerwein rearrangement of a bicyclo[3.1.1]heptanol under mitsunobu conditions

✍ Scribed by P.Andrew Evans; Jade D. Nelson; Arnold L. Rheingold

• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 144 KB
• Volume: 38
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(97)00325-0

✦ Synopsis

Treatment of bicyclo/3.l.l]heptanoanoll under stanokd Mitsunobu conditions afforded after hydrolysis the rearranged bicyclo[2.2.l]hep~l2 in 80% overall yield 0 1997 Elsevier %kxx Ltd. The skeletal rearrangement of naturally derived terpenes, such as fl-pinene, has intrigued synthetic chemists for many years.' Indeed, this has prompted detailed mechanistic and theoretical studies into the factors that are responsible for these important rearrangements. Electrophilic, photochemical, radical and thermal methods have been employed to effect the structum.l morganizuion of B-pinene type skeletons via a series of complementary rearrangement pathways.*2 In this paper, we report a novel Wagner-Meerwein rearran gement3 of the bicyclo[3.1.l]heptanol 1 skeleton, under Mitsunobu conditions for the synthesis of a new rigid enantiomerically pure scaffold (scheme 1).4,5 Scheme 1 QH NHTS