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Samarium(II) iodide-mediated reductive cyclization approach to total synthesis of the insect sex Attractant (−)-anastrephin

✍ Scribed by Kin-ichi Tadano; Yoshiaki Isshiki; Masaki Minami; Seiichiro Ogawa


Publisher
Elsevier Science
Year
1992
Tongue
French
Weight
280 KB
Volume
33
Category
Article
ISSN
0040-4039

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✦ Synopsis


Abstracti Intramolecular reductive cyclization of enantiomerically pure. y,y-differentially C-substituted a&unsaturated ester 5 having a terminal aldehyde functionality, was effectively achieved using SmI2 in THF-HMF'A.

Starting with the major cyclization product 6. enantiospecific total synthesis of (-)-anastrephin 1 was completed.

Owing to their potency to create a carbon-carbon bond, reductive coupling reactions mediated by lanthanides such as Sm(I1) iodide have been extensively investigated in recent years.1

Applications of the SmI2-mediated reductive coupling reactions to substrates having two carbonyl functionalities in the molecules can provide tiveand six-membered carbocycles.

We have studied currently several approaches to enantiomerically pure carbocycles.2 Herein, we report result of the SmI2-mediated intramolecular reductive coupling reaction of a D glucose-derived substrate such as 5. 3 The major product obtained by the reductive cyclization 6 could be