Carbon-silicon-switch effect in enantioselective construction of silicon-stereogenic center from silacyclohexadienones DOI Creative Commons
Yu Yan, Qi Wei, Zhishan Su

et al.

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

Published: Nov. 15, 2024

Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy far less been investigated. Here we discover an unusual effect enantioselective construction silicon-stereogenic center. It is found that there change desymmetrization silacyclohexadienones using asymmetric conjugate addition or oxidative Heck aryl/alkyl nucleophiles when compared their analogues cyclohexadienones. Specifically, leads to reversal enantioselectivity arylzinc as nucleophile same chiral catalyst, results totally different arylboronic acid nucleophile. Control experiments density theory (DFT) calculations have shown comes from unique stereoelectronic feature silicon. Silicon incorporated into place under principle that, given they belong periodic group, could be similar. Here, authors perform desymmetrizations on silacyclohexenone analogue, two substrates yielding opposite enantiomers, showing our understanding similarities atoms incomplete.

Language: Английский

Chiral Aldehyde/Palladium Catalysis Enables Asymmetric Branched-Selective Ring-Opening Functionalization of Methylenecyclopropanes with Amino Acid Esters DOI
Fang Zhu, Hui He, Wen Wei

et al.

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

Published: Jan. 10, 2025

Achieving catalytic asymmetric functionalization of methylenecyclopropanes (MCPs) by selective C–C bond cleavage is a notable challenge due to the intricate reaction partners involved. In this work, we report that chiral aldehyde/palladium combined catalysis enables MCPs with NH2-unprotected amino acid esters. This proceeds through regiospecific branched ring-opening mechanism, resulting in optically active α,α-disubstituted α-amino esters bearing nonconjugated terminal alkene units. Mechanism studies indicate pathways are irreversible and ultimate regioselectivity governed palladium catalysis. The products can be utilized construction dihydropyrazoles, α-methyl aspartic derivatives, analogues VPC01091 BMS-986104.

Language: Английский

Citations

2
Enantioselective 1,4-Borylamination via Copper-Catalyzed Cascade Hydroborylation and Hydroamination of Arylidenecyclopropanes DOI

Yu-Shen Zhu,

Yuecong Guo, Yingying Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32283 - 32291

Published: Nov. 13, 2024

Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, natural products, but their catalytic enantioselective synthesis remains rarely explored. We report the first 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation hydroamination of arylidenecyclopropanes. This combines four readily available components in highly chemo-, site-, fashion (>20:1 r.r. up to 99% ee), yielding diverse array synthetically valuable enantioenriched 4-amino alkylboronates. The versatile utility these products is highlighted by transformations wide applications pharmaceutical discovery. Preliminary mechanistic studies were conducted elucidate operative pathway, intermediates, origins its high chemo- site-selectivity.

Language: Английский

Citations

6
Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C–C Bond Cleavage DOI
Jie Zhao,

Deyue Ren,

Jintao Xia

et al.

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

Published: Jan. 28, 2025

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C–C bond activation via oxidative addition transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters MCPs to produce α-allylated 2H-pyrrole derivatives. In this reaction, azomethine ylide formed by chiral copper catalyst with ketimine ester would serve as nucleophile react activated palladium catalysis. This bimetallic system exhibited broad substrate scope high regio- enantioselectivities.

Language: Английский

Citations

0
Nickel(0)-Catalyzed Stereospecific and Enantioselective Ring-Opening Hydrosilylation of Methylenecyclopropanes to Access (E)-Homoallylsilanes DOI
Ji Zhang, Jiawei Guo, Wanlin Liu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3126 - 3133

Published: Feb. 6, 2025

Language: Английский

Citations

0
Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes DOI
Wenrui Zheng, Yuhan Cao,

Boon Beng Tan

et al.

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

Published: March 25, 2025

Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly controllable ring-retaining ring-opening reactions, is rarely explored. Considering utility enantioenriched organoboronate compounds, herein we report ligand-controlled copper-catalyzed hydroboration dihydroboration reactions arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos (S,S)-Ph-BPE employed, respectively. Mechanistic studies reveal process via β-C elimination significantly slower than arylidenecyclopropanes presence CuOAc (S,S)-Ph-BPE. The these two protocols further demonstrated through conducting various stereospecific site-selective transformations organoboron products, including concise synthesis bioactive molecules.

Language: Английский

Citations

0
Catalytic Reductive (Double) [4+1] Sila-cycloaddition of 1,3-Dienes with Di-, Tri-, and Tetrachlorosilane(s) Enabled by the Pyridine–Diimine–Nickel Complex DOI

Ye-Fei Zhang,

Li Li, Yong Tang

et al.

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

Published: April 7, 2025

Herein, we report a catalytic reductive [4+1] sila-cycloaddition between functionalized 1,3-dienes and chemical feedstock di-, tri-, tetrachlorosilane(s), enabled by cost-effective pyridine-diimine-nickel complex, providing practical method to prepare diverse silacyclopent-3-enes in up 92% yield, including bridged spiro silacarbocycles. This reaction demonstrates broad substrate compatibility, with different substitution patterns more accessible E/Z isomeric mixture. Notably, trichlorosilanes undergo tandem sila-cycloadditions/nucleophilic substitutions, while tetrachlorosilane successfully performs double sila-cycloadditions 2 equiv of directly construct

Language: Английский

Citations

0
Modular and Regioselective Synthesis of Eight-Membered Benzosilacycles Enabled by Ring Expansion of Silacyclobutanes with Aryl Halides and Alkynes DOI
Zhenzhen Guo, Jinxiang Ye, Yingying Zhang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7066 - 7078

Published: April 16, 2025

Language: Английский

Citations

0
Cobalt-Catalyzed Regioselective Intramolecular Hydrosilylation of Olefins to Access Sila-heterocycles DOI

Teng‐Teng Wu,

Zilu Wang,

Yun‐He Xu

et al.

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

Published: April 25, 2025

An efficient and straightforward cobalt-catalyzed regioselective intramolecular hydrosilylation of olefins has been developed. Regioselectivity is controlled by the choice ligands substrates, which operate through two distinct mechanisms. This method successfully applied to both terminal internal alkenes phenyl alkyl tethers between silane alkene, demonstrating its versatility across a broad range substrates.

Language: Английский

Citations

0
Pd-Catalyzed Hydrocyanation of Methylenecyclopropanes: A Highly Selective Ring-Opening Access to 2-Substituted Allylic Nitriles DOI

Mingdong Jiao,

Haijun Fang,

Jianxi Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9431 - 9435

Published: Oct. 30, 2024

Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient selective palladium-catalyzed hydrocyanation give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that may undergo Markovnikov-type hydrometalation β-carbon elimination.

Language: Английский

Citations

2
Rhodium-catalyzed synthesis of Si-stereogenic alkoxysilanes and silyl enol ethers via hydrosilylation of carbonyl compounds DOI
Yang Ding, Jie Ke, Wenbin Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(93), P. 13734 - 13737

Published: Jan. 1, 2024

An efficient catalytic asymmetric hydrosilylation of aldehydes, ketones, and α,β-unsaturated ketones toward Si-stereogenic alkoxysilanes silyl enol ethers is developed.

Language: Английский

Citations

1