Manganese(I)-Catalyzed Enantioselective Alkylation To Access P-Stereogenic Phosphines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

This work introduces a novel Mn(I)-catalyzed enantioselective alkylation methodology that efficiently produces wide array of P-chiral phosphines with outstanding yields and enantioselectivities. Notably, the exceptional reactivity Mn(I) complexes in these reactions is demonstrated by their effective catalysis both typically reactive alkyl iodides bromides, as well less chlorides. approach broadens accessibility to various simplifies synthesis chiral tridentate pincer concise 1–2 step process, contrary conventional, labor-intensive multistep procedures. Importantly, development significantly expands applicability earth-abundant Mn(I)-based beyond recently established roles catalytic hydrogenative conjugate addition reactions, emphasizing potential viable alternative noble metal chemistry and, some cases, even surpassing performance.

Language: Английский

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Understanding Catalytic Enantioselective C–H Bond Oxidation at Nonactivated Methylenes Through Predictive Statistical Modeling Analysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2110 - 2123

Published: Jan. 22, 2025

Enantioselective C(sp3)-H bond oxidation is a powerful strategy for installing functionality in rich molecules. Site- and enantioselective of strong C-H bonds monosubstituted cyclohexanes with hydrogen peroxide catalyzed by aminopyridine manganese catalysts combination alkanoic acids has been recently described. Mechanistic uncertainties nonobvious enantioselectivity trends challenge development the full potential this reaction as synthetic tool. Herein, we apply predictive statistical analysis to identify mechanistically informative correlations that provide valuable understanding will guide future optimization reactions.

Language: Английский

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Kinetic Resolution of Amino Acids by Phosphine Oxide Catalyzed Enantioselective Esterification

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: May 7, 2025

The first highly efficient kinetic resolution (KR) of racemic amino acids with L-pyroglutaminol as an esterification reagent was reported through a novel phosphine oxide organocatalyst catalyzed under mild conditions, which provides wide range chiral esters and recovered excellent stereoselectivities (s > 1057). catalyst demonstrated stereocontrol catalytic activity, presumably benefited from intimate double H-bonding interaction between the pyroglutaminol core catalyst. Chiral find applications versatile building blocks in synthesis functional molecules, source information asymmetric tools to expand explore function native biological machinery.^1–8 Therefore, represent class valuable indispensable compounds whose stereoselective is major objective within synthetic chemists biologists.^9–10 To best our knowledge, array effective strategies for construction have been developed, such hydrogenation nucleophilic addition imines^11–18, enantioselective carbene insertion into N-H bonds amines or amides^19–23, photobiocatalytic cross-coupling^24–27, stereocontrolled 1,3-nitrogen migration carboxylic acids²⁸. However, identifying specific reaction not always easy task. An alternative well-established strategy relies on KR mixture (Fig. 1a).^29–31 stands out one most practical straightforward obtaining enantioenriched molecules recovering starting materials, effectively allowing access both enantiomers single enantiomer Numerous processes developed that reliably deliver enantiopure compounds, including alcohols^32–36, monohydrosilanes³⁷, organoperoxides³⁸, alkynes^39–40, sulfonyl ketones⁴¹, amines⁴², imines⁴³, sulfoximines^44–45, aldehydes⁴⁶, phosphindane oxides^47–48, heterocyclic compounds^49–52. Despite this significant progress field, remains challenging task has rarely explored.^53–57

Language: Английский

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