Davenport Research Laboratories, Department of Chemistry , University of Toronto , Toronto , Canada , M5S 3H6.
Org Lett. 2019 Sep 20;21(18):7549-7553. doi: 10.1021/acs.orglett.9b02819. Epub 2019 Sep 6.
The rhodium-catalyzed asymmetric ring opening reaction of oxabicyclic alkenes is shown to be an efficient method for synthesizing chiral heterocycles. We demonstrate that the pairwise combination of chiral catalyst with chiral amino-acid-derived pronucleophiles results in a stereodivergent synthesis of diastereomeric hydroxyesters. A favorable conformational preference induces the subsequent lactonization of one diastereomer leading to the highly enantioselective synthesis of oxazinones.
铑催化的氧杂双环烯烃的不对称开环反应是一种合成手性杂环的有效方法。我们证明，手性催化剂与手性氨基酸衍生的亲核试剂的成对组合导致非对映异构体选择性的羟基酯的立体发散合成。有利的构象偏好诱导一种非对映异构体的后续内酯化，从而导致高度对映选择性的恶嗪酮合成。
