Enantioselective Synthesis of α-Allyl Amino Esters via Hydrogen-Bond-Donor Catalysis

被引：43

作者：

Bendelsmith, Andrew J. ^{[1
]}

Kim, Seohyun Chris ^{[1
]}

Wasa, Masayuki ^{[1
]}

Roche, Stephane P. ^{[2
]}

Jacobsen, Eric N. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

[2] Florida Atlantic Univ, Dept Chem & Biochem, Boca Raton, FL 33431 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 29期

关键词：

PRACTICAL ASYMMETRIC-SYNTHESIS; ENOLATE CLAISEN REARRANGEMENT; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; ACIDS; ALKYLATION; METATHESIS; PEPTIDES; DERIVATIVES; REACTIVITY;

D O I：

10.1021/jacs.9b05556

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of alpha-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible alpha-chloro glycinates. A variety of useful alpha-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% cc) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the alpha-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted S(N)2 mechanism.

引用

页码：11414 / 11419

页数：6

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