Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct
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 r...
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| Materialtyp: | Artikel |
| Språk: | English |
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American Chemical Society (ACS)
2020
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| Länkar: | https://hdl.handle.net/1721.1/124335 |
| _version_ | 1826203314546540544 |
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| author | Liu, Richard Zhou, Yujing Yang, Yang Buchwald, Stephen Leffler |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Liu, Richard Zhou, Yujing Yang, Yang Buchwald, Stephen Leffler |
| author_sort | Liu, Richard |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T12:34:41Z |
| format | Article |
| id | mit-1721.1/124335 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:34:41Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1243352022-10-01T09:53:07Z Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct Liu, Richard Zhou, Yujing Yang, Yang Buchwald, Stephen Leffler Massachusetts Institute of Technology. Department of Chemistry Colloid and Surface Chemistry Biochemistry General Chemistry Catalysis 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. National Institutes of Health (U.S.) (grant GM58160) National Institutes of Health (U.S.) (grant GM58160–17S1) National Institutes of Health (U.S.) (grant GM122483) 2020-03-25T18:20:47Z 2020-03-25T18:20:47Z 2019-01-27 2020-02-19T19:16:34Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/124335 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) en 10.1021/jacs.8b13907 ACS publications 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. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Colloid and Surface Chemistry Biochemistry General Chemistry Catalysis Liu, Richard Zhou, Yujing Yang, Yang Buchwald, Stephen Leffler Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title | Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title_full | Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title_fullStr | Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title_full_unstemmed | Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title_short | Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct |
| title_sort | enantioselective allylation using allene a petroleum cracking byproduct |
| topic | Colloid and Surface Chemistry Biochemistry General Chemistry Catalysis |
| url | https://hdl.handle.net/1721.1/124335 |
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