Mark R. Biscoe
Massachusetts Institute of Technology (NIH post-doctoral fellow) 2005-2008
Columbia University, Ph.D., 2005
Wesleyan University, B.A., 1999
Research in the Biscoe lab involves the study of fundamental organometallic reactivity and mechanism, and the application of these studies to the development of new synthetic strategies. Specifically, we seek to develop new synthetic approaches that enable the rational and reliable manipulation of molecules in three dimensions. In this work, we employ configurationally stable, enantioenriched organometallic nucleophiles as a source of stereogenic carbon centers that can be transferred and manipulated via stereospecific cross-coupling reactions. Currently, transition metal-catalyzed cross-coupling methodologies can be reliably used for the preparation of flat, conjugated molecular subunits, but not for branched (chiral) molecular topologies. Consequently, the development of cross-coupling methods that enable the stereospecific transfer of a stereogenic center would constitute a new approach to asymmetric synthesis. New strategies towards the predictable modification of three-dimensional molecular structure will find immediate applications in medicinal chemistry as well as material science.
25. Ma, Xinghua; Zhao, Haoran; Binayeva, Meruyert; Ralph, Glenn; Diane, Mohamed; Zhao, Shibin; Wang, Chao-Yuan; Biscoe, Mark R.* “A General Approach to Stereospecific Cross-Coupling Reactions of Nitrogen-Containing Stereocenters.” Chem 2020, 6, 781-791.
24. Ralph, Glenn; Biscoe, Mark R.* “Preparation of Enantioenriched Alkylcarbastannatranes via Nucleophilic Inversion of Alkyl Mesylates for Use in Stereospecific Cross-Coupling Reactions.” Organometallics 2019, 38, 3912-3915.
23. Zhao, Shibin; Gensch, Tobias; Murray, Benjamin; Niemeyer, Zachary L.; Sigman, Matthew S.*; Biscoe, Mark R.* “Enantiodivergent Pd-Catalyzed C–C Bond Formation Enabled through Ligand Parameterization.” Science 2018, 362, 670-674.
22. Ma, Xinghua; Diane, Mohamed; Ralph, Glenn; Chen, Christine; Biscoe, Mark R.* “Stereospecific Electrophilic Fluorination of Alkylcarbastannatrane Reagents.” Angew. Chem. Int. Ed. 2017, 56, 12663-12667.
21. Wang, Chao-Yuan; Ralph, Glenn; Derosa, Joseph; Biscoe, Mark R.* “Stereospecific Pd-Catalyzed Acylation of Alkylcarbastannatrane Reagents: A General Alternative to Asymmetric Enolate Reactions.” Angew. Chem. Int. Ed. 2017, 56, 856-860.
20. Wang, Chao-Yuan; Derosa, Joseph; Biscoe, Mark R.* “The Use of Stable, Optically Active Organometallic Nucleophiles in Cross-Coupling Reactions: A New Approach to Asymmetric Synthesis.” Chem. Sci. 2015, 6, 5105-5113.
19. Li, Ling; Zhao, Shibin; Joshi-Pangu, Amruta; Diane, Mohamed; Biscoe, Mark R.* “Stereospecific Pd-Catalyzed Cross-Coupling Reactions of Secondary Alkylboron Nucleophiles and Aryl Chlorides.” J. Am. Chem. Soc. 2014,136, 14027-14030.
18. Li, Ling; Wang, Chao-Yuan; Huang, Rongcai; Biscoe, Mark R.* “Stereoretentive Pd-Catalyzed Stille Cross-Coupling Reactions of Secondary Alkyl Azastannatranes and Aryl Electrophiles.” Nature Chem. 2013, 5, 607-612.
17. Li, Ling; Biscoe, Mark R. "Alkylzinc Cross-Coupling Reactions." In Cross-Coupling and Heck-Type Reactions, Vol. 1; Molander, G., Ed.; Georg Thieme Verlag HG: Stuttgart, 2012.
16. Joshi-Pangu, Amruta; Ma, Xinghua; Diane, Mohammed; Iqbal, Sidra; Kribs, Robert J.; Huang, Richard; Wang, Chao-Yuan; Biscoe, Mark R. J. Org. Chem. 2012, 77, 6629-6633.
15. Joshi-Pangu, Amruta; Biscoe, Mark R.* "The Use of Tertiary Alkyl Nucleophiles in Metal-Catalyzed Cross-Coupling Reactions." Synlett 2012, 23, 1103-1107.
14. Joshi-Pangu, Amruta; Wang, Chao-Yuan; Biscoe, Mark R.* “Nickel-Catalyzed Kumada Cross-Coupling Reactions of Tertiary Alkylmagnesium Halides and Aryl Bromides/Triflates.” J. Am. Chem. Soc. 2011, 133, 8478-8481.
13. Joshi-Pangu, Amruta; Ganesh, Madhu; Biscoe, Mark R.* “Nickel-Catalyzed Negishi Cross-Coupling Reactions of Secondary Alkylzinc Halides and Aryl Iodides.” Org. Lett. 2011, 13, 1218-1221.
12. Biscoe, Mark R.; Buchwald, Stephen L. “The Selective Monoarylation of Acetate Esters and Aryl Methyl Ketones Using Aryl Chlorides.”Org. Lett. 2009, 11, 1773-1775.
11. Lee, Brian K.; Biscoe, Mark R.; Buchwald, Stephen L. “Simple, Efficient Protocols for the Pd-Catalyzed Cross-Coupling Reaction of Aryl Chlorides and Dimethylamine.” Tetrahedron Lett. 2009, 50, 3672-3674 [50th anniversary special issue].
10. Fors, Brett P.; Watson, Donald A.; Biscoe, Mark R.; Buchwald, Stephen L. “A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines.” J. Am. Chem. Soc.2008, 130, 13552-13554.
9. Biscoe, Mark R.; Fors, Brett P.; Buchwald, Stephen L. “A New Class of Easily Activated Palladium Precatalysts for Facile C–N Cross-Coupling Reactions and the Low Temperature Oxidative Addition of Aryl Chlorides.” J. Am. Chem. Soc. 2008, 130, 6686-6687.
8. Biscoe, Mark R.; Barder, Timothy E.; Buchwald, Stephen L. “Electronic Effects on the Selectivity of Pd-Catalyzed C–N Bond-Forming Reactions Using Biarylphosphine Ligands: The Competitve Roles of Amine Binding and Acidity.” Angew. Chem. Int. Ed. 2007, 46, 7232-7235.
7. Ikawa, Takashi; Barder, Timothy E.; Biscoe, Mark R.; Buchwald, Stephen L. “Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation.” J. Am. Chem. Soc. 2007, 129, 13001-13007.
6. Barder, Timothy E.; Biscoe, Mark R.; Buchwald, Stephen L. “Structural Insights into Active Catalyst Structures and Oxidative Addition to (Biaryl)phosphine-Palladium Complexes via Density Functional Theory and Experimental Studies.” Organometallics 2007, 26, 2183-2192.
5. Uyeda, Christopher; Biscoe, Mark; Leplae, Paul; Breslow, Ronald. “Hydrophobically-Directed Selective Reduction of Ketones Using Amine Boranes.” Tetrahedron Lett. 2006, 47, 127-130.
4. Biscoe, Mark R.; Breslow, Ronald. “Oxaziridinium Salts as Hydrophobic Epoxidation Reagents: Remarkable Hydrophobically-Directed Selectivity in Olefin Epoxidation.” J. Am. Chem. Soc. 2005, 127, 10812-10813.
3. Biscoe, Mark R.; Uyeda, Christopher; Breslow, Ronald. “Requirements for Selective Hydrophobic Acceleration in the Reduction of Ketones.” Org. Lett. 2004, 6, 4331-4334.
2. Biscoe, Mark R.; Breslow, Ronald. “Hydrophobically-Directed Selective Reduction of Ketones.” J. Am. Chem. Soc. 2003, 125, 12718-12719.
1. Biscoe, M. R.; Fry, A. J. “Dual Reaction Pathways in the Magnesium-Mediated Synthesis of Aziridines from Benzal Halides and Imines.”Tetrahedron Lett. 2001, 42, 2759-2762.