Complex stereochemical course of the mitsunobu “inversion” of allylic alcohols

✍ Scribed by Vittorio Farina

• Book ID: 104212298
• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 260 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)70640-x

✦ Synopsis

The Mitsunobu esterificafion reaction of dicycZopentadienoZs yields mixtures of inversion and retention products. Deuteriwn iabeling demonstrates variable levels of aZZyZic rearrangement.

The Mitsunobu esterification procedure has recently become a very important and useful tool in 1 organic synthesis

. Its stereochemical outcome is almost invariably a clean inversion at the 2 hydroxyl-bearing carbon

. In connection with an ongoing synthetic program, allylic acetate 2 (see Eq.1) was required. 3

The precursor of choice was I, easily obtained by Se02 oxidation of endo-dicyclopentadiene

. When submitted to a standard Mitsunobu protocol (AcOH, DEAU, PPh3, THF,rt) however,