Abstract

Palladium- and nickel-catalyzed cross-coupling reactions serve as extremely powerful tools in organic chemistry, and they been applied to the total synthesis of a wide array of biologically active targets, including apoptolidin, discodermolide, gambierol, palytoxin, ristocetin aglycone, and taxol. During the upcoming grant period, this program will explore a new dimension of cross-coupling reactions-processes that involve alkyl electrophiles as substrates. Efforts will focus on the development of versatile catalysts, including chiral catalysts, for carbon-carbon bond-forming transformations such as the Suzuki, Negishi, Hiyama, Stille, and Sonogashira reactions. Mechanistic studies will play an important role in this project, since an improved understanding of metal-based reactivity should greatly facilitate catalyst development.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM062871-06
Application #
7039241
Study Section
Medicinal Chemistry Study Section (MCHA)
Program Officer
Schwab, John M
Project Start
2001-04-01
Project End
2009-03-31
Budget Start
2006-04-01
Budget End
2007-03-31
Support Year
6
Fiscal Year
2006
Total Cost
$480,672
Indirect Cost

  Institution

Name
Massachusetts Institute of Technology
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
001425594
City
Cambridge
State
MA
Country
United States
Zip Code
02139

  Publications

Wang, Zhaobin; Bachman, Shoshana; Dudnik, Alexander S et al. (2018) Nickel-Catalyzed Enantioconvergent Borylation of Racemic Secondary Benzylic Electrophiles. Angew Chem Int Ed Engl 57:14529-14532
Wang, Zhaobin; Yin, Haolin; Fu, Gregory C (2018) Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins. Nature 563:379-383
Choi, Junwon; Fu, Gregory C (2017) Transition metal-catalyzed alkyl-alkyl bond formation: Another dimension in cross-coupling chemistry. Science 356:
Mu, Xin; Shibata, Yu; Makida, Yusuke et al. (2017) Control of Vicinal Stereocenters through Nickel-Catalyzed Alkyl-Alkyl Cross-Coupling. Angew Chem Int Ed Engl 56:5821-5824
Kalek, Marcin; Fu, Gregory C (2017) Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species. J Am Chem Soc 139:4225-4229
Fu, Gregory C (2017) Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Processes. ACS Cent Sci 3:692-700
Schmidt, Jens; Choi, Junwon; Liu, Albert Tianxiang et al. (2016) A general, modular method for the catalytic asymmetric synthesis of alkylboronate esters. Science 354:1265-1269
Zuo, Zhiwei; Cong, Huan; Li, Wei et al. (2016) Enantioselective Decarboxylative Arylation of ?-Amino Acids via the Merger of Photoredox and Nickel Catalysis. J Am Chem Soc 138:1832-5
Chu, Crystal K; Liang, Yufan; Fu, Gregory C (2016) Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles. J Am Chem Soc 138:6404-7
Liang, Yufan; Fu, Gregory C (2015) Nickel-Catalyzed Alkyl-Alkyl Cross-Couplings of Fluorinated Secondary Electrophiles: A General Approach to the Synthesis of Compounds having a Perfluoroalkyl Substituent. Angew Chem Int Ed Engl 54:9047-51

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