Regio‐ and Diastereoselective Synthesis of Trisubstituted Alkenes Through Hydroalkylation of Alkynyl Boronamides DOI

Langxuan Yang,

Gojko Lalić

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(39)

Published: July 8, 2024

Abstract Hydroalkylation of alkynes is a powerful method for alkene synthesis. However, regioselectivity has been difficult to achieve in transformations internal hindering applications the synthesis trisubstituted alkenes. To overcome these limitations, we explored using boryl groups as versatile directing that can control hydroalkylation and subsequently be replaced cross‐coupling reaction. The result our exploration nickel‐catalyzed alkynyl boronamides provides access wide range alkenes with high regio‐ diastereoselectivity. reaction accomplished variety coupling partners, including primary secondary alkyl iodides, α‐bromo esters, α‐chloro phthalimides, boronic esters. Preliminary studies mechanism provide evidence hydrometalation formation radical intermediates.

Language: Английский

Stereodivergent access to non-natural α-amino acids via enantio- and Z / E -selective catalysis DOI
Panpan Li, Zheng En, Guanlin Li

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6712), P. 972 - 979

Published: Aug. 29, 2024

The precise control of

Language: Английский

Citations

12
High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides DOI Open Access

Yougen Xu,

Ya-Dong Gao,

Lebin Su

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 10, 2023

A novel and convenient approach that combines high-throughput experimentation (HTE) with machine learning (ML) technologies to achieve the first selective cross-dimerization of sulfoxonium ylides via iridium catalysis is presented. variety valuable amide-, ketone-, ester-, N-heterocycle-substituted unsymmetrical E-alkenes are synthesized in good yields high stereoselectivities. This mild method avoids use diazo compounds characterized by simple operation, step-economy, excellent chemoselectivity functional group compatibility. The combined experimental computational studies identify an amide-sulfoxonium ylide as a carbene precursor. Furthermore, comprehensive exploration reaction space also performed (600 reactions) model for yield prediction has been constructed.

Language: Английский

Citations

19
Data Science Guided Multiobjective Optimization of a Stereoconvergent Nickel-Catalyzed Reduction of Enol Tosylates to Access Trisubstituted Alkenes DOI

Natalie P. Romer,

Daniel S. Min,

Jason Y. Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4699 - 4708

Published: March 13, 2024

Herein we report a method for stereoconvergent synthesis of trisubstituted alkenes in two steps from simple ketone starting materials. The key step is nickel-catalyzed reduction the corresponding enol tosylates that predominantly relies on monophosphine ligand to direct formation either E- or Z-trisubstituted alkene products. Reaction optimization was accomplished using data science workflow including training set design, statistical modeling, and multiobjective Bayesian optimization. campaign significantly improved access both products up ∼90:10 diastereoselectivity >90% yield. After identifying superior ligands only 25 reactions were required each objective (E- Z-isomer formation) converge reaction parameters search space ∼30,000 potential conditions EDBO+ platform. Additionally, hierarchical machine learning model developed predict stereoselectivity untested achieve validation mean absolute error (MAE) 7.1% selectivity (0.21 kcal/mol). Ultimately, present synergistic leveraging integration optimization, thereby expanding stereodefined alkenes.

Language: Английский

Citations

8
Enantioselective Synthesis of Cyclopropanes via CuH-Catalyzed Intramolecular Hydroalkylation DOI

Giovanni Lonardi,

S Franco,

Mattia Sartorello

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8730 - 8738

Published: May 21, 2024

A Cu-catalyzed cyclopropanation of γ-bromocrotonate derivatives via a hydrocupration–alkylation sequence is described. This hydroalkylation process good generality and allows access to chiral cyclopropanes bearing aryl, heteroaryl, N-indole, alkenyl, alkyl substituents, all with complete trans-diastereoselectivity, enantioselectivities up >99:1 er, high yields. An experimental computational mechanistic analysis was undertaken, which provided full understanding the factors affecting reaction's diastereo- enantioselectivity. More specifically, it found that Cu-catalyst drives both conjugate hydride addition alkylation steps reaction enantioselectivity governed by distortion effects metal coordination sphere at diastereomeric TSs.

Language: Английский

Citations

6
(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation DOI
Shao‐Jie Lou, Pan Wang, Xin Wen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(39), P. 26766 - 26776

Published: Sept. 20, 2024

The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- stereoselectivity challenges, typically yielding

Language: Английский

Citations

6
Asymmetric Synthesis of SCF3‐Substituted Alkylboronates by Copper‐Catalyzed Hydroboration of 1‐Trifluoromethylthioalkenes DOI Creative Commons
Yuki Kojima, Yuji Nishii, Koji Hirano

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: March 13, 2024

Abstract A synthetic method for preparation of optically active trifluoromethylthio (SCF 3 ) compounds by a copper‐catalyzed regio‐ and enantioselective hydroboration 1‐trifluoromethylthioalkenes with H‐Bpin has been developed. The hydrocupration an in situ generated CuH species subsequent boration reaction generate chiral SCF ‐containing alkylboronate, which Bpin moiety can be further transformed to deliver various molecules. Computational studies suggest that the group successfully controls regioselectivity reaction.

Language: Английский

Citations

4
CuH-Catalyzed Regio- and Enantioselective Formal Hydroformylation of Vinyl Arenes DOI
Subhash Garhwal, Yuyang Dong, Binh Khanh

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 13733 - 13740

Published: May 9, 2024

A highly enantioselective formal hydroformylation of vinyl arenes enabled by copper hydride (CuH) catalysis is reported. Key to the success method was use mild Lewis acid zinc triflate promote formation oxocarbenium electrophiles through activation diethoxymethyl acetate. Using newly developed protocol, a broad range arene substrates underwent efficient hydroacetalization reactions provide access enantioenriched α-aryl acetal products in good yields with exclusively branched regioselectivity. The could be converted corresponding aldehydes, alcohols, and amines full preservation enantiomeric purity. Density functional theory studies support that key C-C bond-forming event between alkyl intermediate electrophile takes place inversion configuration Cu-C bond backside S

Language: Английский

Citations

4
New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes DOI
Shenghan Teng,

Peiyao Liang,

Jianrong Steve Zhou

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Language: Английский

Citations

0
Asymmetric Construction of a SeCF3-Substituted Stereocenter by CuH-Catalyzed Hydroboration of 1-SeCF3-Alkenes DOI

Haruka Matsui,

Yuki Kojima, Kosuke Yasui

et al.

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

Published: Feb. 20, 2025

A copper hydride (CuH)-catalyzed regio- and enantioselective hydroboration of 1-trifluoromethylseleno (SeCF3)-alkenes with H-Bpin has been developed. The hydrocupration an in situ generated CuH species is followed by a boration reaction to successfully construct SeCF3- Bpin-substituted chiral carbon center. key success the appropriate choice tBu-modified biphosphine ligands, which enables overwhelming high efficiency.

Language: Английский

Citations

0
Synthesis of Trisubstituted Alkenes Bearing a Quaternary Carbon by Lewis-Acid Catalyzed Regioselective Reaction of Internal Alkynols with 2-Pyrrolylanilines DOI
Srinivasarao Yaragorla, Avinash Kumar

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

Substituted alkenes, crucial in organic chemistry, are typically accessed from internal alkynes by using transition-metal catalysis. Herein, we report a novel approach to the Lewis acid-catalyzed synthesis of trisubstituted alkenes bearing quaternary carbon alkynols and 2-pyrrolyl arylamines. This method involves allene formation followed intramolecular [5 + 1] annulation furnish diverse range with excellent regioselectivity poor diastereoselectivity. Further, demonstrated gram-scale synthetic transformations proposed reaction mechanism based on isolation intermediates.

Language: Английский

Citations

0