Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct
Name
nihms-1014716.pdf
Description
Accepted version
Size
937.35 KB
Format
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Checksum (MD5)
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Author(s)
Liu, Richard
Zhou, Yujing
Yang, Yang
Buchwald, Stephen Leffler
Date Issued
January 27, 2019
Journal
ACS publications
Publisher
American Chemical Society (ACS)
Citation
Liu, Richard Y., Yujing Zhou, Yang Yang and Stephen L. Buchwald. "Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct." ACS publications 141 (2019):2251-2256 © 2019 The Author(s)
Version
Author's final manuscript
Abstract
Allene (C₃H₄) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis. Meanwhile, the addition of an allyl group (C₃H₅) to ketones is among the most common and prototypical reactions in synthetic chemistry. Herein, we report that the combination of allene gas with inexpensive and environmentally benign hydrosilanes, such as PMHS, can serve as a replacement for stoichiometric quantities of allylmetal reagents, which are required in most enantioselective ketone allylation reactions. This process is catalyzed by copper catalyst and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of this catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied directly. Based on our strategy, we anticipate the rapid development of methods that leverage this unexploited feedstock as an allyl anion surrogate.
Subjects
Colloid and Surface Chemistry
Biochemistry
General Chemistry
Catalysis
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/jacs.8b13907
