Synthesis of the C6-C18 bis-tetrahydrofuran fragment of the proposed structure of iriomoteolide-2a via stepwise double S(N)2 cyclization reactions

Zhang, Wen1,2,3; Ma, Haichen1; Li, Chuang-Chuang2,3; Dai, Wei-Min1

2019-03-22

10.1016/j.tet.2018.12.038

TETRAHEDRON   影响因子和分区

0040-4020

The C6-C18 bis-tetrahydrofuran (bis-THF) fragment of the proposed structure of iriomoteolide-2a has been synthesized via stepwise double intramolecular S(N)2-type etherifications. The C11 and 06 stereogenic centers could be secured in the forms of propargyl alcohols by asymmetric transfer hydrogenation of the corresponding propargyl ketones. The C9-C12 THF ring was first constructed via a tandem asymmetric dihydroxylation (AD)-S(N)2 sequence while the C13-C16 THF ring was later installed via an intramolecular S(N)2 reaction of a chiral propargyl mesylate. During the latter THF ring formation, epimerization at the propargylic carbon was not observed. Since the initially proposed (9R,11S,12R) configuration of iriomoteolide-2a has recently been revised to (9S,11R,12S), the established synthesis of the C6-C18 bis-THF fragment could be easily amended by using the opposite enantiomers of the chiral ligands for AD and asymmetric transfer hydrogenation. (C) 2018 Elsevier Ltd. All rights reserved.

Alkynones Asymmetric dihydroxylation Asymmetric transfer hydrogenation Bis-tetrahydrofuran Intramolecular S(N)2 reaction Iriomoteolide-2a

SCI ; CPCI-S ; IC ; CCR

英语

其他

Research Grant Council, The Hong Kong Special Administrative Region, P. R. China[16300016]

Chemistry

Chemistry, Organic

WOS:000462418900031

PERGAMON-ELSEVIER SCIENCE LTD

CHEMISTRY

Web of Science

1.Hong Kong Univ Sci & Technol, Dept Chem, Lab Adv Catalysis & Synth, Kowloon, Clear Water Bay, Hong Kong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China

Zhang, Wen,Ma, Haichen,Li, Chuang-Chuang,et al. Synthesis of the C6-C18 bis-tetrahydrofuran fragment of the proposed structure of iriomoteolide-2a via stepwise double S(N)2 cyclization reactions[J]. TETRAHEDRON,2019,75(12):1795-1807.

Zhang, Wen,Ma, Haichen,Li, Chuang-Chuang,&Dai, Wei-Min.(2019).Synthesis of the C6-C18 bis-tetrahydrofuran fragment of the proposed structure of iriomoteolide-2a via stepwise double S(N)2 cyclization reactions.TETRAHEDRON,75(12),1795-1807.

Zhang, Wen,et al."Synthesis of the C6-C18 bis-tetrahydrofuran fragment of the proposed structure of iriomoteolide-2a via stepwise double S(N)2 cyclization reactions".TETRAHEDRON 75.12(2019):1795-1807.