Diastereoselective Overman Rearrangement of an L‐Ascorbic‐Acid‐Derived Allylic Alcohol: Application in the Synthesis of (+)‐1, 2‐Di‐epi‐swainsonine and a Tetrahydroxypyrrolizidine1. Issue 13 (20th March 2015)

• Record Type: Journal Article
• Authors: Rajasekaran, Parasuraman; Ansari, Alafia A.; Vankar, Yashwant D.
• Is Part Of: European journal of organic chemistry. Issue 13(2013)
• Page Start: 2902
• Page End: 2913
• Publication Date: 2015-03-20
• Subjects: Iminosugars -- Nitrogen heterocycles -- Alkaloids -- Sigmatropic rearrangement -- Diastereoselectivity -- Cyclization -- Metathesis; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201500129
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Differently substituted ascorbic‐acid‐derived allylic alcohols were used to study the Overman rearrangement under thermal and palladium‐catalysed conditions. It was found that protection of the δ alcohol substituent as a a tert ‐butyldimethylsilyl ether followed by Overman rearrangement using PdCl2 (MeCN)2 and p ‐benzoquinone at room temperature gave the best yield of the rearranged product in a highly diastereoselective manner. This rearrangement has been applied in the synthesis of (+)‐1, 2‐di‐ epi ‐swainsonine and a tetrahydroxypyrrolizidine. Abstract : Syntheses of (+)‐1, 2‐di‐ epi ‐swainsonine and a tetrahydroxypyrrolizidine are reported from anL ‐ascorbic‐acid‐derived allylic alcohol through a diastereoselective Overman rearrangement.