SPSiPs, a Class of Diphosphine Ligands Based on SPSiOL with a Large Dihedral Angle

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3859 - 3863

Published: May 22, 2023

The development and the synthetic applications of a novel class diphosphine ligands (SPSiPs) based on chiral spirosilabiindane diol (SPSiOL) are presented. Starting from SPSiOL, could be readily prepared in three steps with high efficiency. This features rigid configuration, large dihedral angle, P-M-P long P-P distance. potentials SPSiPs asymmetric catalysis have also been preliminarily disclosed.

Language: Английский

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

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

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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

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

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection well‐defined sila‐synthons, development more convenient and economic method with readily available starting materials is significantly less explored remains considerable challenge. Herein, we report first example copper‐catalyzed sequential hydrosilylation accessible methylenecyclopropanes (MCPs) primary silanes, affording an efficient route to wide range chiral silacyclopentanes bearing consecutive silicon‐ carbon‐stereogenic excellent enantio‐ diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine intermolecular ring‐opening aryl MCPs intramolecular asymmetric resultant Z / E mixture homoallylic silanes.

Language: Английский

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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

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

Published: April 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Language: Английский

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Selective Hydrosilylation and Hydroboration of Allenes Catalyzed by Cobalt‐Pincer Complexes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(12), P. 2775 - 2783

Published: April 24, 2024

Abstract Achieving precise control over regioselectivity and stereoselectivity in the hydroelementation of terminal allenes presents a formidable challenge. Despite existence various catalytic methods for their functionalization, this entire class reactions remains significantly underdeveloped demands extensive research. Here, we report method using inexpensive PN 5 P pincer cobalt complexes built on triazine backbone. Depending substituent at ring, enables selective synthesis E‐alkenylsilane or Z‐allylborane derivatives. In presented approach, silanes pinacoloboranes play dualistic role simultaneous activator substrate excluding need addition external bases. Finally, application potential obtained compounds was demonstrated by performing further functionalizations compounds.

Language: Английский

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Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6735 - 6778

Published: Jan. 1, 2024

The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.

Language: Английский

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Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration

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

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Nickel-Catalyzed Mono- and Dihydrosilylation of Aliphatic Alkynes in Aqueous and Aerobic Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5077 - 5087

Published: March 20, 2024

1,1-Disilanes are synthetically versatile building blocks, owing to their low toxicity, high stability, and unique structures. However, the practical synthesis of 1,1-disilanes is still a challenge. Despite available Fe-, Co-, La-, B-catalyzed protocols, use highly reactive reductants, such as EtMgBr, NaBHEt3, or KHMDS, inevitably requires air- moisture-free conditions. Herein, we report homogeneous Ni-catalyzed mono- dihydrosilylation aliphatic terminal alkynes under either air water conditions neat conditions, affording β-(E)-vinylsilanes in yields with complete regioselectivity stereoselectivity. Importantly, our method gram-scalable sole example alkynes. We demonstrated introduction different silyl groups through stepwise addition each silane source reaction vessel. Furthermore, intermediates were characterized spectroscopic/spectrometric tools, density functional theory calculations performed understand mechanism origins for 1,1-disilanes.

Language: Английский

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Synthesis of (Z)-Allylsilanes by Cu-Catalyzed Regioselective Protosilylation of Allenes via a Single-Electron Process

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2380 - 2388

Published: Jan. 25, 2025

Language: Английский

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