P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

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Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9713 - 9723

Published: July 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Language: Английский

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Cobalt-catalyzed enantioselective C–H/N–H annulation of aryl sulfonamides with allenes or alkynes: facile access to C–N axially chiral sultams

Chemical Science, Journal Year: 2023, Volume and Issue: 14(26), P. 7291 - 7303

Published: Jan. 1, 2023

Herein we report a cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes and alkynes, using either chemical or electrochemical oxidation. By O2 as the oxidant, proceeds efficiently low catalyst/ligand loading 5 mol% tolerates wide range allenes, including 2,3-butadienoate, allenylphosphonate, phenylallene, resulting in C-N axially chiral sultams high enantio-, regio-, position selectivities. The alkynes also exhibits excellent enantiocontrol (up to >99% ee) variety functional sulfonamides, internal terminal alkynes. Furthermore, oxidative is achieved simple undivided cell, demonstrating versatility robustness cobalt/Salox system. gram-scale synthesis asymmetric catalysis further highlight practical utility this method.

Language: Английский

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N,O-Auxiliary Enabled Cobaltaelectro-Catalyzed Atroposelective C–H Annulation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 1 - 9

Published: Dec. 7, 2023

Herein, we disclosed an efficient synthesis of C–N axially chiral pyridine-N-oxides through cobalt-catalyzed enantioselective C–H activation and annulation under electro-oxidative conditions. This protocol is accomplished by using a readily available cobalt(II) catalyst salicyloxazoline (Salox) ligand in undivided cell. The combination electrochemical simple Co/Salox system enabled effective control over the chemo- enantioselectivity process. A broad range benzamides alkynes bearing diverse functional groups are well compatible to deliver products with high yields enantioselectivities (up 97% yield 99% ee). scalability, asymmetric application, transformations demonstrated synthetic practicality. Moreover, photoluminescence properties further highlight potential applications this strategy material development performance enhancement.

Language: Английский

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Enantioselective C–H bond functionalization under Co(iii)-catalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3354 - 3369

Published: Jan. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Language: Английский

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Metal-free construction of dihydropyrazino[2,3-b]indoles from 2-aminoacetophenones, isocyanates and 1,2-diamines

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(10), P. 2043 - 2048

Published: Jan. 1, 2024

A Brønsted acid/iodine co-mediated approach to construct dihydropyrazino[2,3-

Language: Английский

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Electrochemical enabled cobalt catalyzed enantioselective C-H acyloxylation of aryl phosphamide with carboxylic acid

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8323 - 8329

Published: Jan. 1, 2024

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Language: Английский

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Parametrization of κ²-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4450 - 4459

Published: Feb. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Language: Английский

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Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Language: Английский

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