Research in the Jamison Group

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Ni-Cat C–C Bond Formation

   Metal-catalyzed reactions continue to see widespread use in academic settings as well as in the pharmaceutical industry and for the synthesis of commodity chemicals. As such, a major area of research in the Jamison group is the development of transition-metal-catalyzed methods for the formation of carbon–carbon and carbon–heteroatom bonds with high regio-, diastereo-, and enantioselectivity. These efforts involve nickel(0) catalysts supported by phosphines, phosphites, and N-heterocyclic carbenes for the synthesis of complex molecules from simple feedstocks such as alkynes, α-olefins, epoxides, and aldehydes.

   The Jamison Laboratory is active in the development of substitution reactions employing simple alkenes as alkenyl metal equivalents. Nickel-catalyzed intermolecular benzylation, heterobenzylation, and allylation (not shown) of unactivated alkenes proceed with high yields and high functional-group tolerance. In contrast to analogous palladium-catalyzed variants, these reactions employ electronically unbiased aliphatic olefins, proceed at room temperature, and provide 1,1-disubstituted olefins with high selectivity.


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   We have recently become interested in developing new, air-stable nickel precatalysts to further facilitate the use of the nickel-catalyzed methods we have developed, as well as further enable the development of new transformations. One solution we have devised is precatalyst 1, a low-cost and easy-to-access nickel(II) complex that can be applied to a number of nickel-catalyzed transformations.

   When 1 is used as the nickel source for the benzylation of terminal alkenes, no glovebox is necessary to set up the reaction, and even degassing and drying of reagents is no longer necessary.  When Ni(cod)2 is used as the nickel source for this reaction, air and water must be rigorously excluded, as is almost universally the case when using Ni(cod)2. Additionally, the absence of 1,5-cyclooctadiene causes a significant enhancement of the rate of reaction and allows the catalyst loading to be reduced by a factor of two or more.

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   Another major area of research within our group is the development of Ni-catalyzed reductive coupling reactions, leading to the formation of highly enantioenriched allylic or homoallylic alcohols and amines, both of which are valuable intermediates in organic synthesis. For an overview of much of our work in the area of reductive couplings, see Pure Appl. Chem. 2008, 80, 929-939 (alkene couplings) and Chem. Commun. 2007, 4441-4449 (alkyne couplings).

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   Recently, we have demonstrated that isopropanol serves as an effective reducing agent for the Ni-catalyzed reductive coupling reactions of alkynes and epoxides. This important advance obviates the requirement for triethylborane and allows the use of air-stable and inexpensive Ni(II) salts in place of Ni(cod)2. Deuterium-labeling studies demonstrated that oxidative addition of an in situ-generated Ni(0) species proceeds at the least hindered C–O bond of the epoxide with inversion of configuration.

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Representative Publications:
  • Tasker, S. Z.; Gutierrez, A. C.; Jamison, T. F. “Nickel-Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products,” Angew. Chem. Int. Ed. 2014, 53, 1858-1861.Download PDF
  • Standley, E. A. and Jamison, T. F. “Simplifying Nickel(0) Catalysis: An Air-Stable Nickel Precatalyst for the Internally Selective Benzylation of Terminal Alkenes” J. Am. Chem. Soc. 2013, 135, 1585-1592. Download PDF
  • Matsubara, R.; Gutierrez, A. C.; Jamison, T. F. “Nickel-Catalyzed Heck-Type Reactions of Benzyl Chlorides and Simple Olefins” J. Am. Chem. Soc. 2011, 133, 19020-19023. Download PDF
  • Beaver, M. G.; Jamison, T. F. “Ni(II) Salts and 2-Propanol Effect Catalytic Reductive Coupling of Epoxides and Alkynes” Org. Lett. 2011, 13, 4140-4143. Download PDF
  • Liu, P.; McCarren, P.; Cheong, P. H.-Y.; Jamison, T. F.; Houk, K. N. "Origins of Regioselectivity and Alkene-Directing Effects in Nickel-Catalyzed Reductive Couplings of Alkynes and Aldehydes" J. Am. Chem. Soc. 2010, 132, 2050-2057. Download PDF
  • McCarren, P. R. Liu, P.; Cheong, P. H.-Y.; Jamison, T. F.; Houk, K. N. "Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions" J. Am. Chem. Soc. 2009, 131, 6654-6655. Download PDF
  • Ng., S.-S.; Ho, C.-Y.; Jamison, T. F. "Nickel-Catalyzed Coupling of Alkenes, Aldehydes, and Silyl Triflates" J. Am. Chem. Soc. 2006, 128, 11513-11528. Download PDF
  • Molinaro, C; Jamison, T. F. "Catalytic Reductive Coupling of Epoxides and Aldehydes: Epoxide Ring Opening Precedes Carbonyl Reduction" Angew. Chem., Int. Ed. 2005, 44, 129-132. Download PDF
  • Miller, K. M.; Luanphaisarnnont, T.; Molinaro, C.; Jamison, T. F. "Alkene-Directed, Nickel-Catalyzed Coupling Reactions of Alkynes" J. Am. Chem. Soc. 2004, 126, 4130-4131. Download PDF
  • Miller, K. M.; Huang, W.-S.; Jamison, T. F. "Catalytic Asymmetric Reductive Coupling of Alkynes and Aldehydes: Enantioselective Synthesis of Allylic Alcohols and α-Hydroxy Ketones" J. Am. Chem. Soc. 2003, 125, 3442-3443. Download PDF