Cross- and branched-selective hydroalkenylation by metal hydride selection.
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| Title: | Cross- and branched-selective hydroalkenylation by metal hydride selection. |
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| Authors: | Li, Chunyu (AUTHOR), Gan, Xu-cheng (AUTHOR), Irie, Yu (AUTHOR), Smith, Milo A. (AUTHOR), Shenvi, Ryan A. (AUTHOR) |
| Source: | Science. 3/19/2026, Vol. 391 Issue 6791, p1262-1268. 7p. |
| Subjects: | Hydrides, Nickel catalysts, Coupling reactions (Chemistry), Acids, Alkenylation, Abstraction reactions |
| Abstract: | Controlled placement of branch points along carbon chains is a core capability in the synthesis of materials, agrochemicals, and pharmaceuticals. Metal hydride hydrogen atom transfer (MHAT) to alkenes represents a valuable elementary step because it accesses branched products directly from abundant α-olefins. MHAT catalysis can also be coupled to secondary transition metal catalytic cycles that would otherwise deliver nonbranched (linear) products. However, the hydridic reagents used in MHAT do not always discriminate between the MHAT catalyst and the secondary metal, leading to mixtures of metal hydrides and, therefore, mixtures of products. In this work, we show that a combination of a lutidinium acid and manganese, a weak reductant, selectively generates cobalt hydrides in the presence of a nickel catalyst. We applied these conditions to a cross-selective alkene-alkene coupling that produces valuable branched materials with exquisite selectivity. Editor's summary: A recent trend in synthetic chemistry has been to pair two different catalysts in cooperative coupling reactions. The challenge with these approaches is that there is typically one targeted pathway but numerous ways things can go wrong. Li et al. showcased the subtle balancing act necessary to use cobalt and nickel together to couple two different olefins selectively without running into interfering activity from the product. The key was to use a lutidinium acid and manganese reductant with just the right properties to stay on target. —Jake S. Yeston [ABSTRACT FROM AUTHOR] |
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| Database: | Psychology and Behavioral Sciences Collection |
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| Abstract: | Controlled placement of branch points along carbon chains is a core capability in the synthesis of materials, agrochemicals, and pharmaceuticals. Metal hydride hydrogen atom transfer (MHAT) to alkenes represents a valuable elementary step because it accesses branched products directly from abundant α-olefins. MHAT catalysis can also be coupled to secondary transition metal catalytic cycles that would otherwise deliver nonbranched (linear) products. However, the hydridic reagents used in MHAT do not always discriminate between the MHAT catalyst and the secondary metal, leading to mixtures of metal hydrides and, therefore, mixtures of products. In this work, we show that a combination of a lutidinium acid and manganese, a weak reductant, selectively generates cobalt hydrides in the presence of a nickel catalyst. We applied these conditions to a cross-selective alkene-alkene coupling that produces valuable branched materials with exquisite selectivity. Editor's summary: A recent trend in synthetic chemistry has been to pair two different catalysts in cooperative coupling reactions. The challenge with these approaches is that there is typically one targeted pathway but numerous ways things can go wrong. Li et al. showcased the subtle balancing act necessary to use cobalt and nickel together to couple two different olefins selectively without running into interfering activity from the product. The key was to use a lutidinium acid and manganese reductant with just the right properties to stay on target. —Jake S. Yeston [ABSTRACT FROM AUTHOR] |
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| ISSN: | 00368075 |
| DOI: | 10.1126/science.aeb2389 |
