Biomimetically inspired total synthesis of (12S)-12-hydroxymonocerin and (12R)-12-hydroxymonocerin

• Published in: Tetrahedron Vol. 69; no. 51; pp. 11025 - 11030
• Main Authors: Fang, Bowen, Xie, Xingang, Jing, Peng, Zhao, Changgui, Li, Huilin, Ma, Haichen, She, Xuegong
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 23.12.2013; Elsevier
• Subjects: (12R)-12-Hydroxymonocerin; (12S)-12-Hydroxymonocerin; Anion Relay Chemistry; Asymmetry; biomimetic synthesis; Biomimetically inspired total synthesis; Biomimetics; chemical structure; Chemistry; Chemistry, Organic; cis-Fused furobenzopyranone; Construction; organic compounds; Oxidation; Physical Sciences; Science & Technology; Synthesis; Tetrahedrons; Trapping; Biomimetically inspired total synthesis; Anion Relay Chemistry; OAWLQCWPKLOBPA-ZFIUTFFNSA-N; cis-Fused furobenzopyranone; OAWLQCWPKLOBPA-PCAXDNMNSA-N; (12S)-12-Hydroxymonocerin; CTBVOZQAEMTFPC-RDPSFJRHSA-N; NSLIMGZQJJVQAV-HNNXBMFYSA-N; VRCPTOFPQDPRCW-XSPYEYLBSA-N; (12R)-12-Hydroxymonocerin; SIHHWTUPGAGKIH-RTFZILSDSA-N; FGZVMXMHQMDDKH-LSJOCFKGSA-N; VRCPTOFPQDPRCW-ONVGCPIPSA-N; GCLUDJSUSNHSSF-OZXSUGGESA-N; WVMFPEWOYMGWKR-ZFIUTFFNSA-N; RPFUONAJZSPXGD-UHFFFAOYSA-N; ACXLBGODZLDXST-OYDLWJJNSA-N; GQQDVTHQOQZIKP-SSKFGXFMSA-N; METABOLITES; MONOCERIN; DIVERSITY-ORIENTED SYNTHESIS; CONSTRUCTION; SILYL DITHIANES; PHOSPHORIC ACID; (+)-MONOCERIN; MULTICOMPONENT LINCHPIN COUPLINGS; ASYMMETRIC TOTAL-SYNTHESIS
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2013.09.075

A concise asymmetric total synthesis of (12S)-12-hydroxymonocerin (1) and (12R)-12-hydroxymonocerin (2) were efficiently achieved from the known 4-bromo-2,6-dimethoxyphenol. The synthetic approach was inspired by our biomimetic synthesis of (+)-monocerin (3) and 7-O-demethylmonocerin (4). The cis-fused furobenzopyranones of 1 and 2 was efficiently constructed via an intramolecular nucleophilic trapping of a quinonemethide intermediate, which was obtained by benzylic oxidation of compound 10 using 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). [Display omitted]