Stereoselective synthesis of dipeptides by asymmetric reduction of dehydropeptides catalyzed by chiral rhodium complexes

Meyer, Dominique; Poulin, Jean-Claude; Kagan, Henri B.; Levine‐Pinto, H.; Morgat, J. L.; Fromageot, P.

doi:10.1021/jo01311a026

Cited by 58 publications

(7 citation statements)

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“…32 Studying the mechanism of Rh-catalyzed hydrogenation has provided insights with far-reaching impact in catalysis, such as enantioselective control (Knowles and Noyori), 33,34 Curtin-Hammett selectivity (Halpern), 23 and chiral amplification (Kagan). 35,36 In the context of hydrogenation, our report showcases the first example of a sequential and stereoselective mechanism. These insights highlight the potential of molecular recognition in organic synthesis and provides a foundation for the construction of cyclic peptides by cascade catalysis.…”

Section: Discussionmentioning

confidence: 71%

Hydrogenation catalyst generates cyclic peptide stereocentres in sequence

Hansen

Khan

et al. 2018

Nature Chem

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Molecular recognition plays a key role in enzyme-substrate specificity, the regulation of genes, and the treatment of diseases. Inspired by the power of molecular recognition in enzymatic processes, we sought to exploit its use in organic synthesis. Here we demonstrate how a synthetic rhodium-based catalyst can selectively bind a dehydroamino acid residue to initiate a sequential and stereoselective synthesis of cyclic peptides. Our combined experimental and theoretical study reveals the underpinnings of a cascade reduction that occurs with high stereocontrol and in one direction around a macrocyclic ring. As the catalyst can dissociate from the peptide, the C to N directionality of the hydrogenation reactions is controlled by catalyst-substrate recognition rather than a processive mechanism in which the catalyst remains bound to the macrocycle. This mechanistic insight provides a foundation for the use of cascade hydrogenations.

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Section: Discussionmentioning

confidence: 71%

Hydrogenation catalyst generates cyclic peptide stereocentres in sequence

Hansen

Khan

et al. 2018

Nature Chem

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“…2-(Deuteriomethyl)-3-methylnaphthalene (4) 7.58 (s, 2, H-1,4), 7.45-7.25 (m, 2, H-6,7), 2.75 (q, J = 7.5 Hz, 2, CH2CH3), 2.42 (s, 3, Ar CH3), 1.30 (t, J = 7.5 Hz, 3, CH2CH3); GC-MS (Cl), m/e 199 ( + 29,8), 171 ( + 1, 100), 170 (M, 90) 169 (M -1,14), 155 (M -15,31).…”

Section: Methodsmentioning

confidence: 99%

Transition-state pliability in nitrogen-to-nitrogen proton transfer

Menger¹,

GROSSMAN²,

Liotta³

1983

J. Org. Chem.

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“…In the homogeneous hydrogenation of dehydrodipeptide derivatives, coordination of the olefin and the amidocarbonyl oxygen to the metal is also anticipated (similar to the reduction of dehydroamino acid derivatives), and this presents the question of whether the reaction proceeds by substrate-control or by catalyst-control. In general, the chiral center in the dehydrodipeptide was found to have little influence on the stereoselectivity, and this small degree of substrate-control enables the synthesis of dipeptides or tripeptides having a desired configuration at will, with the newly forming chiral center being controlled by the external effect of the chiral catalysts [70,71,77,78]. The structure of dehydrodipeptides also influences stereoselectivity, and dehydrodipeptides of the RCO-DAA-AA-OR' type can be hydrogenated with high stereoselectivities, while those of the RCO-Gly-DAA-OR' type could be converted with only moderate to good stereoselectivities.…”

Section: Hydrogenation Of Dehydrooligopeptidesmentioning

confidence: 99%