Axial chirality reversal and enantioselective access to Si-stereogenic silylallene

Chem, Journal Year: 2023, Volume and Issue: 9(10), P. 2956 - 2970

Published: July 18, 2023

Language: Английский

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Asymmetric alkyl-alkyl cross-coupling enabled by earth-abundant metal-catalyzed hydroalkylations of olefins

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(4), P. 100508 - 100508

Published: Jan. 30, 2023

Language: Английский

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Copper‐Catalyzed Enantioselective Trifluoromethoxylation of Propargyl Sulfonates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 2, 2023

Due to the strong electron-withdrawing nature and high lipophilicity of trifluoromethoxy group (OCF3 ), methods for introducing OCF3 into organic molecules are in demand. However, research area direct enantioselective trifluoromethoxylation is still embryonic stage, with limited enantioselectivity and/or reaction types. Here, we describe first copper-catalyzed propargyl sulfonates using trifluoromethyl arylsulfonate (TFMS) as source up 96 % ee.

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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Enantioselective alkyl–alkyl coupling by Ni-catalysed asymmetric cross-hydrodimerization of alkenes

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(11), P. 1360 - 1368

Published: July 11, 2024

Language: Английский

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Copper/Chiral Phosphoric-Acid-Catalyzed Intramolecular Reductive Isocyanide-Alkene (1 + 2) Cycloaddition: Enantioselective Construction of 2-Azabicyclo[3.1.0]hexanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7956 - 7962

Published: March 12, 2024

Enantioenriched 2-azabicyclo[3.1.0]hexanes are accessed from readily available allyl substituted α-isocyanoesters by intramolecular (1 + 2) cycloaddition with the olefinic moiety and isocyano carbon as respective C2 C1 units. Cyclopropanation is initiated 1,1-hydrocupration of isocyanide followed formimidoylcopper to copper α-aminocarbenoid equilibration subsequent cycloaddition. The unprecedented copper/chiral phosphoric acid (CPA) catalytic system can be operated in presence water under air, delivering a variety containing an angular all-carbon quaternary stereocenter good excellent yields enantioselectivity.

Language: Английский

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Conjugate Addition of Chiral Allenylcopper Species to Vinyl Bis(sulfone) To Access an All-Carbon Quaternary Center

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Asymmetric formation of all-carbon quaternary centers has been recognized as a challenging area in organic synthesis. Herein, we report copper-catalyzed approach toward coupling two alkenyl substrates, resulting the chiral center. In reaction, axially tetrasubstituted allenylcopper species were generated catalytically and chemoselectively, situ from substituted enynes, remarkably performed an efficient organometallic nucleophile conjugate addition to unsaturated sulfones.

Language: Английский

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Regio- and Stereoselective Copper-Catalyzed Borylation–Protodeboronation of 1,3-Diynes: Access to (Z)-1,3-Enynes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(15), P. 2652 - 2656

Published: April 6, 2023

A facile method to access (Z)-1,3-enynes is realized via sequential copper-catalyzed regio- and stereoselective borylation-protodeboronation of 1,3-diynes. Pinacolborane, copper(II) acetate, Xantphos as the ligand efficiently install hydrogen Bpin in a cis fashion, which followed by rapid hydrolysis with water. The reaction has wide substrate scope occurs chemoselective fashion.

Language: Английский

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

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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Asymmetric alkyl-alkyl cross-coupling enabled by Ni-catalyzed cross-hydrodimerization of enamides with unactivated alkenes

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 28, 2024

Abstract Saturated stereogenic centers containing C(sp3)–C(sp3) bonds comprise a major portion of organic molecules. Over the past decades, transition-metal-catalyzed asymmetric cross-coupling has evolved into an efficient strategy for constructing such centers. However, reaction modes to build remain limited. Herein, nickel-catalyzed enantioselective cross-hydrodimerization between distinct alkenes enable construction alkyl–alkyl been developed. In this mode, N-acyl enamines (enamides) and unactivated undergo oxidative with excellent levels chemo- head-to-tail regioselectivity give enantioenriched α-branched amines by forging bond control enantioselectivity. The presence both reducing oxidizing reagents in allows use as sole precursors forge bonds, representing new mode cross-coupling. provides saturated bonds.

Language: Английский

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