Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes
Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56142-z |
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| author | Li-Zhi Zhang Pei-Chao Zhang Qian Wang Min Zhou Junliang Zhang |
| author_facet | Li-Zhi Zhang Pei-Chao Zhang Qian Wang Min Zhou Junliang Zhang |
| author_sort | Li-Zhi Zhang |
| collection | DOAJ |
| description | Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates remains a challenging and and long-standing goal. Here we report an efficient asymmetric domino Heck/Tsuji−Trost reaction of highly flexible vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, the Heck insertion as stereodetermining step to form ƞ3 allyl palladium complex and in situ trapping with nucleophiles enable efficient Heck/etherification in a formal (4 + 2) cycloaddition manner. Engineering the Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands are vital component in achieving excellent catalytic reactivity and enantioselectivity. This strategy offers a general, modular and divergent platform for rapidly upgrading feedstock flexible vinylic halides and dienes to various value-added molecules and is expected to inspire the development of other challenging enantioselective domino Heck/cross-couplings. |
| format | Article |
| id | doaj-art-c6d66fc9292d4f6aa1fd85fe9def917b |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-c6d66fc9292d4f6aa1fd85fe9def917b2025-01-26T12:42:07ZengNature PortfolioNature Communications2041-17232025-01-011611710.1038/s41467-025-56142-zEnantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienesLi-Zhi Zhang0Pei-Chao Zhang1Qian Wang2Min Zhou3Junliang Zhang4School of Ethnic Medicine, Yunnan Minzu UniversityThe Center for Basic Research and Innovation of Medicine and Pharmacy (MOE), School of Pharmacy, Second Military Medical University (Naval Medical University)College of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of TechnologySchool of Ethnic Medicine, Yunnan Minzu UniversityCollege of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of TechnologyAbstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates remains a challenging and and long-standing goal. Here we report an efficient asymmetric domino Heck/Tsuji−Trost reaction of highly flexible vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, the Heck insertion as stereodetermining step to form ƞ3 allyl palladium complex and in situ trapping with nucleophiles enable efficient Heck/etherification in a formal (4 + 2) cycloaddition manner. Engineering the Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands are vital component in achieving excellent catalytic reactivity and enantioselectivity. This strategy offers a general, modular and divergent platform for rapidly upgrading feedstock flexible vinylic halides and dienes to various value-added molecules and is expected to inspire the development of other challenging enantioselective domino Heck/cross-couplings.https://doi.org/10.1038/s41467-025-56142-z |
| spellingShingle | Li-Zhi Zhang Pei-Chao Zhang Qian Wang Min Zhou Junliang Zhang Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes Nature Communications |
| title | Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes |
| title_full | Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes |
| title_fullStr | Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes |
| title_full_unstemmed | Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes |
| title_short | Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes |
| title_sort | enantioselective heck tsuji trost reaction of flexible vinylic halides with 1 3 dienes |
| url | https://doi.org/10.1038/s41467-025-56142-z |
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