Asymmetric Synthesis of cis‐ and trans‐2‐Aryl‐6‐methylpyrans from D‐Glucose by Arylation and Inversion of Configuration at the C‐2 Position. Issue 1 (15th November 2013)

• Record Type: Journal Article
• Authors: Michigami, Kyosuke; Shimazaki, Atsuko; Hayashi, Masahiko
• Is Part Of: European journal of organic chemistry. Issue 1(2014)
• Page Start: 244
• Page End: 253
• Publication Date: 2013-11-15
• Subjects: Carbohydrates -- Asymmetric synthesis -- Medicinal chemistry -- Oxygen heterocycles -- Arylation -- Deoxygenation -- Chiral pool; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201301376
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Asymmetric synthesis of optically active cis ‐ and trans ‐2‐aryl‐6‐methylpyrans from commercially available tetra‐ O ‐acetyl‐D ‐glucopyranosyl bromide has been developed. The reaction proceeds by two important steps. One is the arylation, and the other is deoxygenation at the C‐3 position and inversion of configuration at the C‐2 position during the preparation of the cis ‐isomer, when 2‐aryl‐3‐hydroxy‐6‐(hydroxymethyl)pyrans were treated with trimethylsilyl chloride and sodium iodide. Abstract : 2‐Aryl‐3‐hydroxy‐6‐(hydroxymethyl)pyrans were synthesized from tetra‐ O ‐acetyl‐D ‐glucopyranosyl bromide by Friedel–Crafts arylation. The pyrans were converted into optically active cis ‐ and trans ‐2‐aryl‐6‐methylpyrans. Treatment of the pyrans with trimethylsilyl chloride and sodium iodide gave cis ‐analogues by deoxygenation at the C‐3 position and inversion of configuration at the C‐2 position