Chiral building-blocks by chemoenzymatic desymmetrization of 2-ethyl-1,3-propanediol for the preparation of biologically active natural products

被引：19

作者：

Izquierdo, I ^{[1
]}

Plaza, MT ^{[1
]}

Rodríguez, M ^{[1
]}

Tamayo, J ^{[1
]}

机构：

[1] Univ Granada, Fac Pharm, Dept Organ Chem, E-18071 Granada, Spain

来源：

TETRAHEDRON-ASYMMETRY | 1999年 / 10卷 / 03期

关键词：

D O I：

10.1016/S0957-4166(99)00020-8

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

2-Ethyl-1,3-propanediol 1 and its related di-O-acetate 2 were desymmetrized by partial chemoenzymatic acetylation and deacetylation, by Pseudomonas fluorescens lipase (Amano P.; PFL), to (R)-1-O-acetyl-2-ethyl-1,3-propanediol 3. On treatment of 3 with I-2/Ph3P/imidazole the related (S)-1-O-acetyl-2-ethyl-3-iodopropanol 4 was obtained and transformed into the corresponding triphenylphosphonium salt 5. Reaction of [(S)-3-acetoxy-2-ethylpropylidene] triphenylphosphorane 6, prepared from 5, with 2,3 :4,5-di-O-isopropylidene-beta-D-arabino-hexos-2-ulopyranose 7 gave (2)-3-C-acetoxymethyl-1,2,3,4,5-pentadeoxy-6,7:8,9-di-O-isopropylidene-beta-D-manno-dec-4-ene-6-ulo-6,10-pyranose 8 which was hydrogenated to 9 and subsequently deacylated to 10. Treatment of 10 with Me2CO/H+ caused a rearrangement to (3R,4R,5S,6R,9R)-9-ethyl-5-hydroxy-3,4-isopropylidenedioxy-1,7-dioxaspiro[5.5]undecane 11, which closely matched the skeleton of the talaromycins. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：449 / 455

页数：7

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