Sulfide Synthesis via A Bioinspired C-S σ-Bond Metathesis.

Journal: Chemistry (Weinheim An Der Bergstrasse, Germany)
Published:
Abstract

In this manuscript, inspired by the natural S-adenosylmethionine (SAM) cycle, we devised a mixed σ-bond metathesis between the (sp3)C-S bond of organic sulfides with the C-O bond of alcohols. This reaction is mediated by a readily available and operationally facile mixture of AlCl3 and ZnI2, which allows fast access to various challenging organic sulfides by directly editing the (sp3)C-S bond of easily available ones. Like multiple bond metathesis, this method could also be rendered intramolecular and extended to ether (sp3)C-O bond metathesis as well as amine (sp3)C-N bond metathesis to provide saturated heterocycles such as cyclic thioethers, cyclic ethers, as well as cyclic amines. Mechanistic experiments and DFT calculations were carried out to show a high level of resemblance to the natural SAM cycle. We anticipate this bioinspired design of C-S/C-O metathesis will infuse the area of a σ-bond metathesis with more insights and provide opportunities for further advances in areas that have been facilitated by traditional C-X bond forming reactions.

Authors
Hongmei Liu, Yuzhu Zheng, Ke-lin Xian, Qi-qi Hu, Rong-zhen Liao, Youwei Xie