Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

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Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

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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Binaphthyl Scaffold: A Class of Versatile Structure in Asymmetric C–H Functionalization

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9359 - 9396

Published: July 18, 2022

Over the past decades, transition metal-catalyzed enantioselective C–H functionalization has emerged as a straightforward and powerful tool for rapid access to chiral molecules. The enormous advances achieved in this emerging area largely rely on development of ligands that can enable both high levels enantiocontrol efficiency. Chiral bearing binaphthyl scaffolds have been proven be versatile asymmetric due their availability, unique stereochemical features, ease fine-tuning steric electronic properties. In Review, we summarized advance applications basis scaffold functionalization.

Language: Английский

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Ru(II)/Chiral Carboxylic Acid-Catalyzed Asymmetric [4 + 3] Annulation of Sulfoximines with α,β-Unsaturated Ketones

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 13876 - 13883

Published: Oct. 27, 2022

Sulfur-stereogenic containing benzo-fused heterocycles have gained much attention in drug discovery. However, the asymmetric synthesis of these chiral molecules with structural diversity is very challenging. Herein, we report benzothiadiazine-1-oxides a seven-membered ring via achiral Ru(II)-catalyzed [4 + 3] annulation sulfoximines α,β-unsaturated ketones assisted by carboxylic acid (CCA). A broad range benzothiadiazepine-1-oxides bearing various functional groups could be prepared up to 90% yield >99% ee, expanding chemical space sulfoximines. Notably, oxidative cleavage double bonds products gave N-benzoyl C–S axis.

Language: Английский

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Sulfoxide-Directed or 3d-Metal Catalyzed C–H Activation and Hypervalent Iodines as Tools for Atroposelective Synthesis

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(3), P. 189 - 202

Published: Jan. 27, 2023

ConspectusThe expanding applications of atropisomeric compounds combined with the growing diversity such chiral molecules translate into an urgent need for innovative synthetic strategies allowing their rapid, efficient, and sustainable synthesis. Recently, C-H activation approach has provided new opportunities synthesizing axially compounds. The two complementary approaches implementation methodology toward synthesis imply either ortho-functionalization preexisting prochiral or atropo-unstable biaryl substrates direct arylation sterically encumbered aromatics. first required preinstallation a directing group on precursor, which drastically limits thus generated products. To tackle this important limitation, we have envisioned using sulfoxide as both auxiliary. Indeed, in addition to efficiently coordinating Pd-catalyst induction, moiety can be easily removed, via sulfoxide/lithium exchange, after step, guaranteeing almost unlimited postdiversification efficiency generality concept could illustrated by developing atropo-diastereoselective oxidative Heck reaction, acetoxylation, iodination, well arylation. Besides, utility was demonstrated designing expedient steganone precursor. This unique transformation also allowed us build up unprecedented triaryl scaffolds perfectly controlled axes, original skeletons ligand design. While considering atroposelective arylations, clear antagonism between harsh reaction conditions frequently coupling hindered atropo-stability product, resulted scarcity transformations. solve fundamental challenge, focused application low-valent cobalt catalyst, prompted catalyze indoles at C2 position under extremely mild (room temperature). Accordingly, C2-arylation achieved carbene delivering uncommon atropoisomerically pure excellent yields enantioselectivities. Detailed experimental theoretical mechanistic studies shed light mechanism transformation, providing strong evidence regarding origin enantioselectivity. Finally, steric hindrance guarantee molecule couple partners is limitation not only development but C-N Despite long history incredible advances Ullmann-Goldberg Buchwald-Hartwig couplings, versions transformations remained until recently. Our idea challenging issue consisted hypervalent iodines highly reactive partners, desired N-arylations occur room temperature. hypothesis validated reporting Cu-catalyzed N-arylation, λ3-iodanes partners. Subsequently, enantioselective version N-arylation successfully established Cu-complex bearing BOX ligand. In conclusion, report herein tailored-made solutions provide construct molecules, including biaryls molecules.

Language: Английский

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Simple Ether‐Directed Enantioselective C(sp³)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Language: Английский

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Palladium(II)-Catalyzed Enantioselective Functionalization of C(sp³)—H Bonds^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(11), P. 1522 - 1522

Published: Jan. 1, 2023

Chiral molecules are ubiquitous in nature and play an important role natural products, pharmaceuticals, agriculture, advanced materials, as well living organisms.Therefore, the development of efficient strategies to enable facile construction enantiopure chiral compounds atom-and step-economical manner is great importance.The enantioselective functionalization C-H bonds without multi-steps transformation arguably one most powerful straightforward fulfill this goal.This emerging research field has been rapidly developed with innovation various catalysts and/or ligands recent years.In particular, significant advances have achieved palladium-catalyzed C(sp 3 )-H bonds, streamlining concise from readily available hydrocarbon feedstocks.The stereoselective assistance ligand form a palladacycle intermediate, which could be transformed into chemical functionalized compounds, attracted tremendous attention.Thus, perspective summarizes on palladium(II)-catalyzed via asymmetric palladation.According type classified several sections, including methyl methylene constrained cycloalkanes, adjacent α-heteroatom, benzylic unbiased bonds.The emphasis focuses discussion philosophy developing novel mode stereocontrol.The remaining limitations challenges regarding chemo-and control also discussed.Further new catalytic systems expected address these issues expands scope synthetic strategy.We anticipate that might inspire more efforts strategy find wide applications synthesis complicated molecules, such products drugs.

Language: Английский

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Ligand‐Enabled Palladium(II)‐Catalyzed Enantioselective β‐C(sp³)−H Arylation of Aliphatic Tertiary Amides**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 5, 2023

Amide is one of the most widespread functional groups in organic and bioorganic chemistry, it would be valuable to achieve stereoselective C(sp3 )-H functionalization amide molecules. Palladium(II) catalysis has been prevalently used C-H activation chemistry past decades, however, due weakly-coordinating feature simple amides, challenging their direct with enantiocontrol by PdII catalysis. Our group developed sulfoxide-2-hydroxypridine (SOHP) ligands, which exhibited remarkable activity Pd-catalyzed C(sp2 activation. In this work, we demonstrate that chiral SOHP ligands served as an ideal solution enantioselective amides. Herein, report efficient asymmetric /SOHP-catalyzed β-C(sp3 arylation aliphatic tertiary ligand plays a key role deprotonation-metalation step.

Language: Английский

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