Axially Chiral Ligands and Catalysts Derived from Atropisomeric Binaphthyl Structures DOI
Shouyi Cen, Zhipeng Zhang

Published: Oct. 18, 2024

The synthesis of 1,1′-bi-2-naphthol (BINOL) can be traced back to about 100 years ago, whereas the utilization BINOL as a chiral ligand was reported by Noyori et al. in 1979. One year later 1980, development and application 2,2′-bis(di-phenylphosphino)-1,1′-binaphthyl (BINAP) reported. This milestone brings axially binaphthyl structures stage asymmetric catalysis inspires large variety ligands organocatalysts possessing axial chirality. chapter traces source chirality, focuses on structural diversity catalysts timeline for their development, introduces 150 representative derived from structures, especially BINOL, 2,2′-diamino-1,1′-binaphthalene (BINAM), 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). With rapid syntheses diversified molecules, it is expected that more novel powerful will developed, tremendous transformations realized future.

Language: Английский

Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives DOI

Zhong-Tian Ye,

Zhongwei Wu,

Xue‐Xin Zhang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Language: Английский

Citations

13
Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles DOI

Wan‐Er Gan,

Yong‐Shun Wu,

Bin Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 5, 2024

Abstract A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and formation. In addition, kinetic resolution racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the developed afford carbon‐ benzoxasiloles. Ring‐opening reactions chiral with organolithiums Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

Language: Английский

Citations

12
X-type silyl ligands for transition-metal catalysis DOI

Jihui Gao,

Yicong Ge,

Chuan He

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4648 - 4673

Published: Jan. 1, 2024

This review summarizes the developments of X-type silyl ligands for transition-metal catalysis, elucidating unique features σ-donating ability and trans -influence silyl–metal catalysts.

Language: Английский

Citations

10
Organocatalytic Si–CAryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes DOI

Ming Jhang Wu,

Yi‐Wei Chen, Qian Lu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20646 - 20654

Published: Sept. 11, 2023

Chiral organosilanes are valuable chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. As an important strategy for constructing chiral organosilanes, functionalization Si-CAryl bond typically relies on transition-metal catalysis. Herein, we present efficient method atroposelective synthesis biaryl siloxane atropisomers via organocatalytic Si-C dinaphthosiloles with silanol nucleophiles. The reaction proceeds through protonation simultaneous cleavage/silanolysis sequence presence a newly developed Brønsted acid catalyst. versatile nature streamlines derivatization axially products into other atropisomers, thereby expanding applicability this method.

Language: Английский

Citations

21
Cobalt-Catalyzed Asymmetric Reductive Alkenylation and Arylation of Heterobiaryl Tosylates: Kinetic Resolution or Dynamic Kinetic Resolution? DOI
Haiyan Dong, Chuan Wang

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26747 - 26755

Published: Nov. 29, 2023

Herein, we report a cobalt-catalyzed atroposelective reductive cross-coupling of racemic heterobiaryl tosylates with C(sp2)–X type electrophile. Both aryl and alkenyl halides are competent precursors for this reaction, providing variety heterobiaryls as the products in highly enantioselective manner high functionality tolerance. The related asymmetric arylation alkenylation discovered to proceed divergent mechanisms. reaction pathway changes from kinetic resolution (KR) when bromides iodides bearing strong electron-withdrawing substitution on para-position employed starting materials an enantioconvergent transformation via dynamic KR configurationally labile cobaltacycles relatively electron-rich used. change mechanisms turns out arise relative rates two competing elementary steps, which epimerization cyclic Co(I) intermediates their trapping by coupling electrophiles C(sp2)-type oxidative addition.

Language: Английский

Citations

19
Catalytic Asymmetric Synthesis of Unnatural Axially Chiral Biaryl δ‐Amino Acid Derivatives via a Chiral Phenanthroline‐Potassium Catalyst‐Enabled Dynamic Kinetic Resolution DOI
Shouyi Cen, Shanshan Li, Yin Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 15, 2024

Axially chiral biaryl δ-amino acids possess significantly different conformational properties and environment from centrally amino acids, therefore, have drawn considerable attention in the fields of synthetic medicinal chemistry. Herein, a novel phenanthroline-potassium catalyst has been developed by constructing well-organized axially ligand composed one 1,10-phenanthroline unit two 1,1'-bi-2-naphthol (BINOL) units. In presence this catalyst, good to excellent yields enantioselectivities (up 99 % yield, 98 : 2 er) achieved ring-opening alcoholytic dynamic kinetic resolution variety lactams, thereby providing an efficient protocol for catalytic asymmetric synthesis unnatural acid derivatives.

Language: Английский

Citations

7
Rhodium Complexes with a Pyridine-2-yloxy-silyl-Based N,Si-Ligand: Bonding Situation and Activity as Alkene Hydrogenation Catalysts DOI Creative Commons
Alejandra Goméz‐España, Pilar García‐Orduña, Fernando J. Lahoz

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(3), P. 402 - 413

Published: Jan. 23, 2024

Rh(III) complexes [Rh(H)(X)(κ2-NSitBu2OPy)(L)] (X = Cl, L PCy3, 2a; PHtBu2, 2b; X OTf, 3a; 3b) (NSitBu2OPy 4-methylpyridin-2-yloxy-ditertbutylsilyl) have been prepared and characterized by means of elemental analysis nuclear magnetic resonance (NMR) spectroscopy. The solid-state structures 2a, 2b, 3a determined X-ray diffraction studies. Computational analyses the bonding situation these species evidence electron-sharing nature Rh–Si bond significant role electrostatic component in interaction between transition metal fragment [Rh(H)(PR3)(X)]• [NSitBu2OPy]• ligand. In addition, a comparative study activity 3a, 3b, related iridium as catalysts for hydrogenation olefins has performed. best catalytic results obtained when using with triflate PCy3 ligands, catalyst. density functional theory studies show that formation alkane is thermodynamically favored rate-limiting step corresponds to hydrogen activation, which takes place via σ-complex-assisted metathesis mechanism.

Language: Английский

Citations

5
Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration DOI
Yufeng Shi, Ying Qin, Zhong‐Qiu Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: July 30, 2024

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction silicon-stereogenic architectures by functionalization has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed enantioselective silylmethyl involving aryl alkyl 1,5-palladium migration naphthalenes possessing enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy note that realization induction at step metal itself remains challenging. Our study constitutes first reaction. The key success discovery and fine-tuning different substituents α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, ensure enantioselectivity desired reactivity.

Language: Английский

Citations

5
Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation DOI Creative Commons
Lei Su,

Shen Gao,

Jiawang Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

Citations

5
Enantioselective construction of silicon-stereogenic vinylsilanes from simple alkenes DOI Creative Commons

Kailin Yin,

Ji Zhang, Deng Pan

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 18, 2025

The diverse utility of acyclic vinylsilanes has driven the interest in synthesis enantioenriched bearing a Si-stereogenic center. However, predominant approaches for catalytic asymmetric generation have mainly relied on transition metal-catalyzed reactions alkynes with different silicon sources. Here we successfully realize enantioselective linear silicon-stereogenic good yields and enantiomeric ratios from simple alkenes under rhodium catalysis. significance this transformation lies its ability to achieve regioconvergent enantioconvergent conversion, efficiently transforming petroleum-derived isomeric mixtures olefin feedstocks into single regio- stereoisomer product. practicality method is further exemplified by downstream transformations these leveraging functionality leaving group nature aryl substituent as well development chiral π-conjugated double bond systems.

Language: Английский

Citations

0