Hydrogen Atom Transfer

Hydrogen Atom Transfer2024-07-02T00:06:16+00:00

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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82. On the role of thermally activated EDA complexes in decarboxylative cross-coupling2024-09-12T20:22:14+00:00

82. Dao, N.; Shenvi, R. A. On the role of thermally activated EDA complexes in decarboxylative cross-coupling Tetrahedron 2024 [invited, T. Maimone award issue], accepted.

77.  Carbon Quaternization of Redox Active Esters and Olefins via Decarboxylative Coupling2024-06-28T05:59:33+00:00

77. Gan, X.-c.;† Zhang, B.;† Dao, N.;† Bi, C.; Pokle, M.; Kan, L.; Collins, M. R.; Tyrol, C. C.; Bolduc, P. N.; Nicastri, M.; Kawamata, Y.; Baran, P. S.; Shenvi, R. A. Carbon Quaternization of Redox Active Esters and Olefins via Decarboxylative CouplingScience 2024, 384, 113. †co-first authors

76. Alkene hydrobenzylation by a single catalyst that mediates iterative outer-sphere steps2024-06-28T06:00:41+00:00

76. Kong, L.;† Gan, X.-c.;† van der Puyl-Lovett, V. A.;† Shenvi, R. A. Alkene hydrobenzylation by a single catalyst that mediates iterative outer-sphere stepsJ. Am. Chem. Soc2024, 146, 2351.
ChemRxiv 10.26434/chemrxiv-2023-zw9c2 2023, †co-first authors.

75. Inner- and outer-sphere cross-couplings for high Fsp3 fragments in natural product space2024-06-28T06:02:10+00:00

75. Kotesova, S.; Shenvi, R. A. Inner- and outer-sphere cross-couplings for high Fsp3 fragments in natural product spaceAcc. Chem. Res. 2023, 56, 3089.

73. Iron-catalyzed hydrobenzylation: stereoselective synthesis of (–)-eugenial C2024-06-28T06:04:59+00:00

73. Gan, X.-c.;§ Kotesova, S.;§ Castanedo, A.; Green, S. A.; Møller, S. L. B.; Shenvi, R. A. Iron-catalyzed hydrobenzylation: stereoselective synthesis of (–)-eugenial C. J. Am. Chem. Soc. 2023, 145, 15714. §co-first authors

70. Manganese, iron and cobalt-catalyzed radical olefin hydrofunctionalization2024-06-28T06:09:18+00:00

70. van der Puyl, V. A.; Shenvi, R. A. Manganese, iron and cobalt-catalyzed radical olefin hydrofunctionalization Science of Synthesis, 2.14: Base Metal Catalysis, 2023, Ed. N. Yoshikai.

65.  Stereodivergent attached ring synthesis via non-covalent interactions: a short formal synthesis of merrilactone2024-07-01T23:48:24+00:00

65. Huffman, B. J.; Chu, T.; Hanaki, Y.; Wong, J. J.; Chen, S.; Houk, K. N.; Shenvi, R. A. Stereodivergent attached ring synthesis via non-covalent interactions: a short formal synthesis of merrilactone A Angew. Chem. Int. Ed. 2022, 61, e202114514.

60. Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals2024-06-28T06:24:36+00:00

60. Shevick, S. L.; Wilson, C. V.; Kotesova, S.; Kim, D.; Holland, P. L.; Shenvi, R. A. Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals. Chem. Sci. 2020, 12401–12422.

56. Cycloisomerization of olefins in water2024-06-28T06:27:52+00:00

56. Matos, J. L. M.; Green, S. A.; Chun, Y; Dang, V. Q.; Dushin, R. G.; Richardson, P.; Chen, J. S.; Piotrowski, D. W.; Paegel, B. M.; Shenvi, R. A. Cycloisomerization of olefins in waterAngew. Chem. Int. Ed. 2020, 59, 12998–13003.
ChemRxiv: 10.26434/chemrxiv.11977917.v1

53. Alkene Hydroarylation by Co/Ni Dual Catalysis2024-06-28T06:30:06+00:00

53. Shevick, S. L.; Baker, M. A.; Shenvi, R. A. Alkene Hydroarylation by Co/Ni Dual Catalysis, Cell: Trends in Chemistry2019, 1, 540–541.

52. Chapter 7. Markovnikov Functionalization by Hydrogen Atom Transfer2024-06-28T06:31:34+00:00

52. Matos, J. L. M.; Green, S. A.; Shenvi, R. A. Chapter 7. Markovnikov Functionalization by Hydrogen Atom TransferOrganic Reactions2019, 100, 383–470.

50. Hydroalkylation of Olefins to form Quaternary Carbons2024-06-28T06:33:15+00:00

50. Green, S. A.; Huffman, T. R.; McCourt, R. O.; van der Puyl, V.; Shenvi, R. A. Hydroalkylation of Olefins to form Quaternary Carbons J. Am. Chem. Soc. 2019, 141, 7709-7714.

46. Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes2024-06-28T06:35:42+00:00

46. Matos, J.L.M.; Vásquez-Céspedes, S.; Gu, J.; Oguma, T.; Shenvi, R.A. Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes J. Am. Chem. Soc. 2018, 140, 16976–16981.

45. The High Chemofidelity of Metal-Catalyzed Hydrogen Atom Transfer 2024-06-28T06:36:36+00:00

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

44. Mechanistic Interrogation of Co/Ni-Dual Catalyzed Hydroarylation2024-06-28T06:37:09+00:00

44. Shevick, S. L.; Obradors, C.; Shenvi, R. A. Mechanistic Interrogation of Co/Ni-Dual Catalyzed Hydroarylation J. Am. Chem. Soc. 2018,140, 12056–12068.

43. Iron-Nickel Dual-Catalysis: A New Engine for Olefin Functionalization2024-06-28T06:37:49+00:00

43. Green, S. A.; Vásquez-Céspedes, S.; Shenvi, R. A. Iron-Nickel Dual-Catalysis: A New Engine for Olefin Functionalization. J. Am. Chem. Soc. 2018, 140, 11317–11324

35. Branch-Selective Hydroarylation: Iodoarene-Olefin Cross Coupling2024-06-28T06:42:52+00:00

35. Green, S. A.; Matos, J. L. M.; Yagi, A.; Shenvi, R. A. Branch-Selective Hydroarylation: Iodoarene-Olefin Cross Coupling. J. Am. Chem. Soc. 2016, 138, 12779-12782.

33. Mn, Fe, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins2024-06-28T06:44:12+00:00

33. Crossley, S. W. M.; Martinez, R. M.; Obradors, C.; Shenvi, R. A. Mn, Fe, and Co-Catalyzed Radical Hydrofunctionalizations of OlefinsChem. Rev. 2016, 116, 8912-9000.

30. Synthesis of the Privileged 8-Arylmenthol Class by Radical Arylation of Isopulegol2024-06-28T06:46:18+00:00

30. Crossley, S. W. M.; Martinez, R. M.; Zuluaga, S. G.; Shenvi R. A. Synthesis of the Privileged 8-Arylmenthol Class by Radical Arylation of IsopulegolOrg. Lett. 2016, 18, 2620-2623.

29. An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers2024-06-28T06:46:50+00:00

29. Obradors, C. L.; Martinez, R.; Shenvi, R. A. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom TransfersJ. Am. Chem. Soc. 2016, 138, 4962-4971.

27. Reinventing Radical Reactions2024-06-28T06:48:04+00:00

27. Shenvi, R. A. Reinventing Radical Reactions. SynLett Cluster (Ed. T. Rovis and R. A. Shenvi). 2016, 27, 678-679.

20. Simple, Chemoselective, Catalytic Olefin Isomerization2024-06-28T06:52:28+00:00

20. Crossley, S. W. M.; Barabé, F.; Shenvi, R. A. Simple, Chemoselective, Catalytic Olefin Isomerization. J. Am. Chem. Soc2014, 136, 16788.​

Isomerization pre-catalyst now available from Sigma-Aldrich

18. Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol2024-06-28T06:53:50+00:00

18. Iwasaki, K.; Wan, K. K.; Oppedisano, A.; Crossley, S. W. M.; Shenvi R. A. Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol. J. Am. Chem. Soc. 2014, 136, 1300-1303.

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