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Metal Hydride (MH) Hydrogen Atom Transfer (HAT) (or MHAT). Classical hydrofunctionalization of alkenes requires strong Bronsted acids to form fleeting, high-energy carbocations. In contrast, non-canonical reactions of metal hydrides can hydrofunctionalize alkenes through lower-energy carbon-centered radicals. We proposed that Co, Fe and Mn-catalyzed reactions pioneered by Mukaiyama proceed through Halpern’s HAT mechanistic paradigm, uniting two literature threads that had remained separate for nearly 35 years. We have used our HAT hydrogenation and HAT isomerization to synthesize inaccessible secondary metabolites (drimane, epoxyhumulene-II, α-funebrene, 7,20-diisocyanoadociane). These reactions also have been applied in total syntheses by other groups due to their high chemoselectivity and chemofidelity (see Ref. 10 below). Our group was the first to combine MH HAT catalysis with nickel-catalyzed cross coupling, which circumvents substrate prefunctionalization, uses native functionality and expands the possibilities of each catalytic cycle. Recently, we have shown that this dual catalytic strategy for branched-selective alkene functionalization can be expanded beyond nickel to other metals. For a short course in MHAT, see these slides.

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See publications

  1. Iwasaki, K.; Wan, K. K.; Oppedisano, A.; Crossley, S. W. M.; Shenvi R. A. "Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol", JACS, 2014136, 1300-1303.

  2. Crossley, S. W. M.; Barabé, F.; Shenvi, R. A. "Simple, Chemoselective, Catalytic Olefin Isomerization” JACS, 2014136, 16788.

  3. Green, S. A.; Matos, J. L. M.; Yagi, A.; Shenvi, R. A. “Branch-Selective Hydroarylation: Iodoarene-Olefin Cross Coupling” JACS2016138, 12779. 

  4. Crossley, S.W.M.; Obradors, C.; Martinez, R.M.; Shenvi, R.A. "Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins." Chem. Rev., 2016116, 8912-2000.

  5. Crossley, S.W.M.; Martinez, R.M.; Guevera-Zuluaga, S.; Shenvi, R.A. "Synthesis of the Privileged 8-Arylmenthol Class by Radical Arylation of Isopulegol." Org. Lett., 2016, 18, 2620-2623. 

  6. Obradors, C.; Marinez, R.M.; Shenvi, R.A. "Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers." JACS, 2016138, 4962-4971.

  7. Green, S. A.; Vásquez-Céspedes, S.; Shenvi, R. A. "Iron-Nickel Dual-Catalysis: A New Engine for Olefin Functionalization." JACS2018, 140, 11317–11324.

  8. Shevick, S. L.; Obradors, C.; Shenvi, R. A. "Mechanistic Interrogation of Co/Ni-Dual Catalyzed Hydroarylation." JACS, 2018, 140, 12056–12068.

  9. Matos, J. M.; Vásquez-Céspedes, S.; Gu, J.; Oguma, T.; Shenvi, R. A. “Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes.” JACS, 2018, 140, 16976–16981.

  10. Green, S. A.; Crossley, S. W. M.; Matos, J. L. M.; Vásquez-Céspedes, S.; Shevick, S.; Shenvi, R. A. "The High Chemofidelity of Metal-Catalyzed Hydrogen Atom Transfer." Acc. Chem. Res. 2018, 51, 2628–2640.

  11. Green, S. A.; Huffman, T. R.; McCourt, R. O.; van der Puyl, V.; Shenvi, R. A. "Hydroalkylation of Olefins to form Quaternary Carbons," JACS 2019, 141, 7709–7714.

  12. Shevick, S. L.; Baker, M. A.; Shenvi, R. A. "Alkene Hydroarylation by Co/Ni Dual Catalysis," Cell: Trends in Chemistry, 2019, 1, 540-541.  DOI:10.1016/j.trechm. 2019.06.003.

  13. Matos, J. L. M.; Green, S. A.; Shenvi, R. A. "Markovnikov Functionalization by Hydrogen Atom Transfer," Organic Reactions, 2019, 100, 383–470.

  14. Matos, J. L. M.; Green, S. A.; Chun, Y; Dang, V. Q.; Dushin, R. G.; Richardson, P.; Chen, J.; Piotrowski, D. W.; Paegel, B. M.; Shenvi, R. A. "Cycloisomerization of olefins in water," Angew. Chem. Int. Ed. 202059, 12998–13003.

  15. Shevick, S. L.; Wilson, C. V.; Kotesova, S.; Kim, D.; Holland, P. L.*; Shenvi, R. A.* “Structure and mechanism in M-H atom transfer” Chem. Sci. 2020, 12401–12422. 

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