Molybdenum chloride catalysts for Z-selective olefin metathesis reactions.

Abstract:

:The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

journal_name

Nature

journal_title

Nature

authors

Koh MJ,Nguyen TT,Lam JK,Torker S,Hyvl J,Schrock RR,Hoveyda AH

doi

10.1038/nature21043

subject

Has Abstract

pub_date

2017-02-02 00:00:00

pages

80-85

issue

7639

eissn

0028-0836

issn

1476-4687

pii

nature21043

journal_volume

542

pub_type

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