Synthesis of Methyl 2-[Bis(benzylthio)phosphoryl]acetate as a Novel Horner-Wadsworth-Emmons-Type Reagent and Its Application to the Diastereodivergent Synthesis of (E)- and (Z)-α,β-Unsaturated Esters

被引：0

作者：

Sano, Shigeki ^{[1
]}

Yamada, Shoki ^{[1
]}

Ihara, Takahito ^{[1
]}

Seki, Kazumasa ^{[1
]}

Kitaike, Syuji ^{[1
]}

Nakao, Michiyasu ^{[1
]}

机构：

[1] Tokushima Univ, Grad Sch Pharmaceut Sci, Sho Machi, Tokushima 7708505, Japan

来源：

SYNLETT | 2024年

关键词：

Horner-Wadsworth-Emmons reagent; phosphorus-sulfur bond; alpha; beta-unsaturated esters; diastereodivergent synthesis; olefination; aldehydes; ALDEHYDES;

D O I：

10.1055/a-2347-1027

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Methyl 2-[bis(benzylthio)phosphoryl]acetate has proven to be an efficient Horner-Wadsworth-Emmons (HWE)-type reagent for the diastereodivergent synthesis of (E)- and (Z)-alpha,beta-unsaturated esters. Under the conditions of excess NaHMDS relative to the HWE-type reagent, the HWE-type reactions of methyl 2-[bis(benzylthio)phosphoryl]acetate with various aldehydes afforded the corresponding alpha,beta-unsaturated esters in an E -selective manner in up to 100:0 E / Z ratio. However, when an excess of the HWE-type reagent was used relative to NaHMDS, the stereoselectivity of the HWE-type reactions was dramatically changed from E to Z , yielding an E / Z ratio of up to 2:98.

引用

页码：546 / 550

页数：5

共 2 条

[1] One-Pot O2-Oxidation and the Horner-Wadsworth-Emmons Reaction of Primary Alcohols for the Synthesis of (Z)-α,β-Unsaturated Esters
Ando, Kaori
Takaba, Chika
Kodama, Masahiro
JOURNAL OF ORGANIC CHEMISTRY, 2022, 87 (15) : 9723 - 9728
[2] Highly E-Selective Solvent-Free Horner-Wadsworth-Emmons Reaction for the Synthesis of α-Methyl-α,β-Unsaturated Esters Using Either LiOH•H2O or Ba(OH)2•8H2O
Ando, Kaori
Isomura, Wakana
Uchida, Nariaki
Mori, Kanae
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2022, 95 (06) : 928 - 934

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