Enantioselective Rh‐Catalyzed Hydroboration of Dialkyl Ketone‐Derived Silyl Enol Ethers DOI

Longqing Liu,

Jinbo Zhao, Wenke Dong

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(20)

Published: June 20, 2024

Abstract A Rh‐catalyzed asymmetric hydroboration of dialkyl ketone‐derived silyl enol ethers with HBpin has been developed using a commercially available catalyst and ligand ([RhCl (cod)] 2 MeO‐BIBOP). variety undergo this transformation, providing the corresponding products high enantioselectivity (up to 97 : 3 % er). In addition, utility protocol is demonstrated by versatile transformation chiral borylether range valuable derivatives.

Language: Английский

Enantioselective synthesis of γ-chiral amides via copper-catalyzed reductive relay hydroaminocarbonylation DOI Creative Commons
Yang Yuan, Youcan Zhang, Xiao‐Feng Wu

et al.

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

Published: Aug. 7, 2024

Chiral amides are common and effective structural motifs found in many pharmaceuticals biologically active molecules. Despite their importance, existing synthetic methods predominantly employed for the synthesis of α-amides β-amides. The remote chiral amides, characterized by distal stereocenters, typically requires intricate steps conducted under demanding conditions. Here, we present a general procedure copper-catalyzed enantioselective γ-chiral employing reductive relay hydroaminocarbonylation strategy with trisubstituted allylic benzoates hydroxylamine electrophiles. This approach demonstrates wide substrate scope excellent enantioselectivity regioselectivity, thus providing access to challenging enantioenriched amides. molecules but authors

Language: Английский

Citations

3

Advanced green synthesis: Solvent-free and catalyst-free reaction DOI Creative Commons
Mengyao Li,

Ao Gu,

Jiatong Li

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Language: Английский

Citations

3

Transition Metal Catalyzed Asymmetric Hydroboration of Internal Alkenes DOI Open Access

Hou‐Xiang Lu,

Bi‐Jie Li

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(10), P. 3167 - 3167

Published: Jan. 1, 2022

Transition metal catalyzed asymmetric hydroboration of alkenes is one the most powerful methods to prepare chiral organoboronates, which has attracted extensive attention chemists due its simple raw materials, high atomic economy, diverse structure borated products, etc.The transition enantioselective internal including strained alkene, β-substituted styrenes and bearing a coordinating group summarized.

Language: Английский

Citations

13

Pd(0)-Catalyzed Diastereoselective and Enantioselective Intermolecular Heck–Miyaura Borylation of Internal Enamides for the β-Aminoboronate Ester Synthesis DOI
Chenchen Wang,

Yang Xi,

Tingting Xia

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 418 - 425

Published: Dec. 20, 2023

Miyaura borylation is widely recognized as one of the most reliable methods for constructing an organoboron compound. Reported herein Pd(0)-catalyzed asymmetric three-component Heck–Miyaura with interception internal olefin, aryldiazonium salt, and diboron reagent. This Heck-triggered protocol proceeds in a highly chemoselective, diastereoselective, enantioselective manner, thus allowing expedient construction 1,2-diaryl substituted β-aminoboronate esters derivatives vicinal stereogenic centers. The versatility resulting benzylic boronic allows their further transformation to more-intricate chiral amines.

Language: Английский

Citations

7

Catalytic Enantioselective (3+2) Annulations of Nucleophilic Thioacyl Rh(I)-Carbenes with Achmatowicz Rearrangement Products DOI

Cunzhi Chen,

Kang Lv, You-Wei Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8949 - 8957

Published: May 28, 2024

The cycloaddition and annulation reactions of Achmatowicz rearrangement products (ARPs) are critically important to the construction molecular complexity total synthesis natural products. However, this field is still blemished by shortage enantioselective (3+2) ARPs. Herein, we report highly enantio-, diastereo-, regioselective annulations ARPs with nucleophilic α-thioacyl Rh(I)-carbenes under Rh(I)/(R)-BINAP catalysis, producing bicyclic dihydrothiophenes multiple functionalities, three continuous chiral centers, five prochiral centers in up 97% yields 99:1 er. Mechanistically, migratory insertion following anticoordination suggested determine enantio- regioselectivities accounts for character Rh(I)-carbenes. DFT calculations revealed that enantioinduction originates from steric discrimination (R)- (S)-ARPs ligand.

Language: Английский

Citations

2

Copper‐Catalyzed Regio‐ and Enantioselective Hydroboration of Difluoroalkyl‐Substituted Internal Alkenes DOI Creative Commons

Tao‐Qian Zhao,

Hui Xu, Yuchen Tian

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 10(35)

Published: Oct. 25, 2023

Abstract Catalytic asymmetric hydroboration of fluoroalkyl‐substituted alkenes is a straightforward approach to access chiral small molecules possessing both fluorine and boron atoms. However, enantioselective without elimination has been long‐standing challenge in this field. Herein, copper‐catalyzed difluoroalkyl‐substituted internal with high levels regio‐ enantioselectivities reported. The native carbonyl directing group, copper hydride system, bisphosphine ligand play crucial roles suppressing the undesired fluoride elimination. This atom‐economic protocol provides practical synthetic platform obtain wide scope enantioenriched secondary boronates bearing difluoromethylene moieties under mild conditions. Synthetic applications including functionalization biorelevant molecules, versatile functional group interconversions, preparation difluoroalkylated Terfenadine derivative are also demonstrated.

Language: Английский

Citations

6

Rhodium-Catalyzed Highly Enantioselective Hydroboration of Acyclic Tetrasubstituted Alkenes Directed by an Amide DOI Creative Commons

Hou‐Xiang Lu,

Cheng Wang, Taotao Gao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16194 - 16202

Published: June 4, 2024

Although progress has been made in enantioselective hydroboration of di- and trisubstituted alkenes over the past decades, tetrasubstituted with high diastereo- enantioselectivities continues as an unmet challenge since 1950s due to its extremely low reactivity difficulties simultaneously control regio- stereoselectivity a alkene. Here, we report highly regio-, diastereo-, catalytic diverse acyclic alkenes. The delicate interplay electron-rich rhodium complex coordination-assistance forms adaptive catalyst that effectively overcomes controls stereoselectivity. generality system is exemplified by efficacy across various steric electronic properties.

Language: Английский

Citations

2

Pd-Catalyzed Hydroboration of Vinylarenes with B2pin2 DOI

Yunhui Wan,

Yingpeng Lu,

Yi Ren

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 9056 - 9062

Published: June 10, 2024

A palladium(II)-catalyzed Markovnikov hydroboration of aryl alkenes with readily available bis(pinacolato)diboron (B2pin2) is reported. The reaction proceeded low catalyst loading (0.5 mol %) in the absence N- or P-containing ligands, affording products up to 90% yield. Trifluoracetic acid serves as hydrogen source, enabling synthesis benzylic boronic esters under mild ambient conditions.

Language: Английский

Citations

2

Organocatalytic hydroboration of olefins in pyrrolidinium ionic liquids DOI Creative Commons
Paweł Huninik, Jakub Szyling, Agnieszka Czapik

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(9), P. 3715 - 3722

Published: Jan. 1, 2023

ILs organocatalyzed regioselective hydroboration of alkenes with HBpin provides anti-Markovnikov adducts high yields and selectivity. The system allows catalyst recycling up to 30 runs. Transformations alkylboronic esters are also included.

Language: Английский

Citations

4

Regio- and enantioselective hydrofluorination of internal alkenes via nickel-catalyzed hydrogen atom transfer DOI
Fan Chen, Xiaoyu Zhao,

Weihang Miao

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110239 - 110239

Published: July 1, 2024

Language: Английский

Citations

1