Enzymatic Enantioselective anti-Markovnikov Hydration of Aryl Alkenes

Hui Lin, Yinyin Meng, Na Li, Yanhong Tang, Shuang Dong, Zhongliu Wu, Cuilian Xu, Romas Kazlauskas, Hongge Chen

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

The addition of water to alkenes is an important method for the synthesis of alcohols, but the regioselectivity of acid-catalyzed hydration of terminal alkenes yields secondary alcohols according to Markovnikov's rule, making it difficult to obtain primary alcohols. Here we report a styrene monooxygenase that catalyzes the anti-Markovnikov hydration of the terminal aryl alkenes under anaerobic conditions. This hydration provides primary alcohols in good yields (up to 100 %), excellent anti-Markovnikov regioselectivity (>99 : 1), and good enantiomeric purity (60–83 % ee). Residues Asn46, Asp100, and Asn309 are essential for catalysis suggesting an acid–base mechanism with a carbanion-like intermediate that could account for the anti-Markovnikov regioselectivity. Our work reveals a new enzymatic tool with unusual regioselectivity based on the promiscuous catalytic activity of a monooxygenase.

Original languageEnglish (US)
Article numbere202206472
JournalAngewandte Chemie - International Edition
Volume61
Issue number32
DOIs
StatePublished - Aug 8 2022

Bibliographical note

Funding Information:
We thank the NMR center in the College of Science at Henan Agricultural University for taking NMR spectra. We acknowledge financial support from the National Natural Science Foundation of China (32171472, 22071237), Natural Science Foundation of Henan Province (202300410218), the Key Scientific Research Projects of Higher Education Institutions in Henan Province (21A180006).

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Keywords

  • Biocatalysis
  • Catalytic Promiscuity
  • Enantioselectivity
  • Hydration
  • anti-Markovnikov Regioselectivity

Fingerprint

Dive into the research topics of 'Enzymatic Enantioselective anti-Markovnikov Hydration of Aryl Alkenes'. Together they form a unique fingerprint.

Cite this