Lange Markus, Meyer F Lorenz, Nosovska Olena, Vilotijevic Ivan
Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstrasse 10, 07743 Jena, Germany.
Org Lett. 2023 Dec 29;25(51):9097-9102. doi: 10.1021/acs.orglett.3c03228. Epub 2023 Dec 15.
Silyl carbamates, latent pronucleophile surrogates of carbamates, undergo allylation using allylic fluorides in the presence of common Lewis base catalysts. The reactions are rendered enantioselective in the presence of chiral Lewis base catalysts and produce suitably protected derivatives of enantioenriched chiral β-amino acids. The design of the latent pronucleophile featuring both a silyl group and an electron-deficient carbamate is instrumental in lowering the nucleophilicity of nitrogen and enabling enantioselective allylation in the presence of chiral cinchona alkaloid-based catalysts.
甲硅烷基氨基甲酸酯作为氨基甲酸酯的潜在亲核试剂替代物，在常见的路易斯碱催化剂存在下，能与烯丙基氟化物发生烯丙基化反应。在手性路易斯碱催化剂存在下，该反应具有对映选择性，可生成对映体富集的手性β-氨基酸的适当保护衍生物。同时具有甲硅烷基和缺电子氨基甲酸酯的潜在亲核试剂的设计，有助于降低氮的亲核性，并在手性金鸡纳生物碱基催化剂存在下实现对映选择性烯丙基化反应。
