{"title":"2-[Bis(benzylthio)phosphoryl]acetate 甲酯作为新型 Horner-Wadsworth-Emmons 型试剂的合成及其在 (E)- 和 (Z)-α,β- 不饱和酯的非对映异构合成中的应用","authors":"Shigeki Sano, Shoki Yamada, Takahito Ihara, Kazumasa Seki, Syuji Kitaike, Michiyasu Nakao","doi":"10.1055/a-2347-1027","DOIUrl":null,"url":null,"abstract":"<p>Methyl 2-[bis(benzylthio)phosphoryl]acetate has proven to be an efficient Horner–Wadsworth–Emmons (HWE)-type reagent for the diastereodivergent synthesis of (<i>E</i>)- and (<i>Z</i>)-α,β-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 α,β-unsaturated esters in an <i>E</i>-selective manner in up to 100:0 <i>E</i>/<i>Z</i> 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 <i>E</i> to <i>Z</i>, yielding an <i>E</i>/<i>Z</i> ratio of up to 2:98.</p> ","PeriodicalId":22319,"journal":{"name":"Synlett","volume":null,"pages":null},"PeriodicalIF":1.7000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"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\",\"authors\":\"Shigeki Sano, Shoki Yamada, Takahito Ihara, Kazumasa Seki, Syuji Kitaike, Michiyasu Nakao\",\"doi\":\"10.1055/a-2347-1027\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Methyl 2-[bis(benzylthio)phosphoryl]acetate has proven to be an efficient Horner–Wadsworth–Emmons (HWE)-type reagent for the diastereodivergent synthesis of (<i>E</i>)- and (<i>Z</i>)-α,β-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 α,β-unsaturated esters in an <i>E</i>-selective manner in up to 100:0 <i>E</i>/<i>Z</i> 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 <i>E</i> to <i>Z</i>, yielding an <i>E</i>/<i>Z</i> ratio of up to 2:98.</p> \",\"PeriodicalId\":22319,\"journal\":{\"name\":\"Synlett\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2024-07-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Synlett\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1055/a-2347-1027\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Synlett","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1055/a-2347-1027","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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
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)-α,β-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 α,β-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.
期刊介绍:
SYNLETT is an international journal reporting research results and current trends in chemical synthesis in short personalized reviews and preliminary communications. It covers all fields of scientific endeavor that involve organic synthesis, including catalysis, organometallic, medicinal, biological, and photochemistry, but also related disciplines and offers the possibility to publish scientific primary data.