Publication Date:
2016-04-30
Description:
A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Nguyen, Thach T -- Koh, Ming Joo -- Shen, Xiao -- Romiti, Filippo -- Schrock, Richard R -- Hoveyda, Amir H -- GM-59426/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2016 Apr 29;352(6285):569-75. doi: 10.1126/science.aaf4622.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, USA. ; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. ; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, USA. amir.hoveyda@bc.edu.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/27126041" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
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Chemistry and Pharmacology
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Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
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