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Rhodium catalyzed chelation-assisted C-H bond functionalization reactions.
Acc Chem Res. 2012 Jun 19; 45(6):814-25.AC

Abstract

Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required prefunctionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of prefunctionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and piperidines. We observed complementary reactivity with Rh(III) catalysts and developed an oxidative coupling with unactivated alkenes. Further studies on the Rh(III) catalysts led us to develop methods for the coupling of C-H bonds to polarized π bonds such as those in imines and isocyanates. In several cases the methods that we have developed for chelation-controlled C-H bond functionalization have been applied to the total synthesis of complex molecules such as natural products, highlighting the utility of these methods in organic synthesis.

Authors+Show Affiliations

Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720, USA.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

22148885

Citation

Colby, Denise A., et al. "Rhodium Catalyzed Chelation-assisted C-H Bond Functionalization Reactions." Accounts of Chemical Research, vol. 45, no. 6, 2012, pp. 814-25.
Colby DA, Tsai AS, Bergman RG, et al. Rhodium catalyzed chelation-assisted C-H bond functionalization reactions. Acc Chem Res. 2012;45(6):814-25.
Colby, D. A., Tsai, A. S., Bergman, R. G., & Ellman, J. A. (2012). Rhodium catalyzed chelation-assisted C-H bond functionalization reactions. Accounts of Chemical Research, 45(6), 814-25. https://doi.org/10.1021/ar200190g
Colby DA, et al. Rhodium Catalyzed Chelation-assisted C-H Bond Functionalization Reactions. Acc Chem Res. 2012 Jun 19;45(6):814-25. PubMed PMID: 22148885.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium catalyzed chelation-assisted C-H bond functionalization reactions. AU - Colby,Denise A, AU - Tsai,Andy S, AU - Bergman,Robert G, AU - Ellman,Jonathan A, Y1 - 2011/12/08/ PY - 2011/12/14/entrez PY - 2011/12/14/pubmed PY - 2012/10/18/medline SP - 814 EP - 25 JF - Accounts of chemical research JO - Acc Chem Res VL - 45 IS - 6 N2 - Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required prefunctionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of prefunctionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and piperidines. We observed complementary reactivity with Rh(III) catalysts and developed an oxidative coupling with unactivated alkenes. Further studies on the Rh(III) catalysts led us to develop methods for the coupling of C-H bonds to polarized π bonds such as those in imines and isocyanates. In several cases the methods that we have developed for chelation-controlled C-H bond functionalization have been applied to the total synthesis of complex molecules such as natural products, highlighting the utility of these methods in organic synthesis. SN - 1520-4898 UR - https://www.unboundmedicine.com/medline/citation/22148885/Rhodium_catalyzed_chelation_assisted_C_H_bond_functionalization_reactions_ L2 - https://doi.org/10.1021/ar200190g DB - PRIME DP - Unbound Medicine ER -
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