A Concise Access to Bridged [2,2,1] Bicyclic Lactones with a Quaternary Stereocenter Via Stereospecific Hydroformylation

Overview

Journal Nat Commun

Specialty Biology

Date 2021 Sep 7

PMID 34489434

Citations 2

Authors

Shuailong Li

Zhuangxing Li

Mingzheng Li

Lin He

Xumu Zhang

Hui Lv

Affiliations

Soon will be listed here.

Abstract

Chiral bridged [2,2,1] bicyclic lactones are privileged structural units in pharmaceutics and bioactive nature products. However, the synthetic methods for these compounds are rare. Here we report an efficient method for enantioselective construction of bridged [2,2,1] bicyclic lactones bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/pyridium chlorochromate (PCC) oxidation. By employing a hybrid phosphine-phosphite chiral ligand, a series of cyclopent-3-en-1-ols are transformed into corresponding γ-hydroxyl aldehydes with specific syn-selectivity. Then, hemiacetals form in situ and oxidation with PCC in one-pot affords bridged [2,2,1] bicyclic lactones in high yields and excellent enantiomeric excess. Replacing the hydroxyl group by an ester group, cyclopentanecarbaldehydes with a chiral all-carbon quaternary stereocenter in the γ-position can be generated efficiently.

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