Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine–Borane Cofactor

Morimoto, Mariko; Cao, Wendy; Bergman, Robert G.; Raymond, Kenneth N.; Toste, F. Dean

doi:10.1021/jacs.0c12479

Title: Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine–Borane Cofactor

Journal Article · Wed Jan 20 00:00:00 EST 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c12479· OSTI ID:1839009

Morimoto, Mariko ^[1]; Cao, Wendy ^[1];

^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Supramolecular catalysts emulate the mechanism of enzymes to achieve large rate accelerations and precise selectivity under mild and aqueous conditions. While significant strides have been made in the supramolecular host-promoted synthesis of small molecules, applications of this reactivity to chemoselective and site-selective modification of complex biomolecules remain virtually unexplored. We report here a supramolecular system where coencapsulation of pyridine-borane with a variety of molecules including enones, ketones, aldehydes, oximes, hydrazones, and imines effects efficient reductions under basic aqueous conditions. Furthermore, upon subjecting unprotected lysine to the host-mediated reductive amination conditions, we observed excellent ε-selectivity, indicating that differential guest binding within the same molecule is possible without sacrificing reactivity. Inspired by the post-translational modification of complex biomolecules by enzymatic systems, we then applied this supramolecular reaction to the site-selective labeling of a single lysine residue in an 11-amino acid peptide chain and human insulin.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)

Grant/Contract Number:: AC02-05CH11231; DGE 1752814; S10OD024998

OSTI ID:: 1839009

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 4; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine–Borane Cofactor

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