Nickel/Quinim Enabled Asymmetric Carbamoyl‐Acylation of Unactivated Alkenes DOI
Xianqing Wu, Haiyan Li, Feng He

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(14), P. 1673 - 1678

Published: Feb. 14, 2023

Comprehensive Summary Transition metal‐catalyzed difunctionalization of tethered alkene has emerged as a prevailing tool for the expedient construction synthetically valuable cyclic compounds. However, most efforts have been devoted to reaction styrene‐type substrates due their rigid scaffold and high reactivity. With respect nonaromatic olefin, especially mono‐substituted alkene, still remains largely underdeveloped. Herein, we disclose nickel/Quinim complex TBADT‐cocatalyzed asymmetric carbamoyl‐acylation unactivated on carbamoyl chlorides with diverse aldehydes. The exhibits broad substrate scope good functional group tolerance, well efficiency enantioselectivity. Both monosubstituted 1,1‐substituted alkenes can work either aliphatic or aromatic aldehydes under current protocol, providing convenient access an array medicinally useful chiral γ‐lactams derivatives bearing convertible acyl functionality. This showcases more application possibilities Quinim ligand in future catalytic transformations.

Language: Английский

Electrochemical NiH‐Catalyzed C(sp3)−C(sp3) Coupling of Alkyl Halides and Alkyl Alkenes DOI Open Access
Pengfei Li,

Guangsheng Kou,

Tian Feng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkenes for the construction Csp3 -Csp3 bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late-stage modification natural products drug derivatives. Mechanistic insights offer evidence process. sp3 -carbon-halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

Citations

25
Straightforward synthesis of functionalized γ-Lactams using impure CO2 stream as the carbon source DOI Creative Commons
Yuman Qin, Robin Cauwenbergh, Suman Pradhan

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 22, 2023

Abstract Direct utilization of CO 2 into organic synthesis finds enormous applications to synthesize pharmaceuticals and fine chemicals. However, pure gas is essential achieve these transformations, the purification highly cost energy intensive. Considering this, we describe a straightforward synthetic route for γ-lactams, pivotal core structure bioactive molecules, by using commercially available starting materials (alkenes amines) impure stream (exhaust collected from car) as carbon source. This blueprint features broad scope, excellent functional group compatibility application late-stage transformation existing natural products functionalized γ-lactams. We believe that our strategy will provide direct access γ-lactams in very sustainable way also enhance Carbon Capture Utilization (CCU) strategy.

Language: Английский

Citations

25
Cobalt‐Catalyzed Asymmetric Aza‐Nozaki–Hiyama–Kishi (NHK) Reaction of α‐Imino Esters with Alkenyl Halides DOI

Tingting Xia,

Yinhui Wu,

Jiangtao Hu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 2, 2024

Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.

Language: Английский

Citations

18
Cobalt‐Catalyzed Enantioselective Reductive α‐Chloro‐Carbonyl Addition of Ketimine to Construct the β‐Tertiary Amino Acid Analogues DOI

Tingting Xia,

Wenwen Wu, Xianqing Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: Jan. 22, 2024

β-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, efficient asymmetric synthesis this motif still remains a significant challenge. Herein, we disclose cobalt-catalyzed enantioselective reductive addition reaction ketimine using α-chloro carbonyl compound as radical precursor, providing expedient access to diverse array enantioenriched β-quaternary analogues. This protocol exhibits outstanding enantioselectivity broad substrate scope with excellent functional group tolerance. Preliminary mechanism studies rule out possibility Reformatsky-type confirm involvement species stereoselective process. The synthetic utility has been demonstrated through rapid assembly iterative oligopeptide, showcasing its versatile platform for late-stage modification drug candidates.

Language: Английский

Citations

14
Ligand-Controlled, Nickel-Catalyzed Stereodivergent Construction of 1,3-Nonadjacent Stereocenters DOI
Qi Pan,

Kuai Wang,

Weipeng Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15453 - 15463

Published: May 25, 2024

In contrast to the asymmetric synthesis of molecules with a single stereocenter or 1,2-adjacent stereocenters, simultaneous construction acyclic 1,3-nonadjacent stereocenters via catalyst in an enantioselective and diastereoselective manner remains formidable challenge. Here, we demonstrate diastereodivergent through Ni-catalyzed reductive cyclization/cross-coupling alkene-tethered aryl bromides α-bromoamides, which represents major remaining stereochemical challenge cyclization/difunctionalization alkenes. Using Ming-Phos as ligand, diverse set oxindoles containing were obtained high levels enantio- diastereoselectivity. Mechanistic experiments density functional theory calculations indicate that magnesium salt plays key role controlling Furthermore, another complementary stereoisomeric products constructed from same starting materials using Ph-Phox ligand.

Language: Английский

Citations

13
Ni-catalyzed cross-electrophile alkyl-alkyl coupling reactions DOI Creative Commons

Li-Xu You,

Tian Lan,

Chunling Guo

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: Английский

Citations

2
Carbamoyl Fluoride-Enabled Enantioselective Ni-Catalyzed Carbocarbamoylation of Unactivated Alkenes DOI
Yue Li,

Feng-Ping Zhang,

Rong-Hua Wang

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(47), P. 19844 - 19849

Published: Nov. 10, 2020

A carbamoyl fluoride-enabled enantioselective Ni-catalyzed carbocarbamoylation of unactivated alkenes was developed, providing a broad range chiral γ-lactams bearing an all-carbon quaternary center in 45–96% yield and 38–97% ee.

Language: Английский

Citations

60
Recent developments in asymmetric Heck type cyclization reactions for constructions of complex molecules DOI
A. N. Reznikov, М. А. Ashatkina, Yu. N. Klimochkin

et al.

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(26), P. 5673 - 5701

Published: Jan. 1, 2021

Intramolecular carbometallation-initiated asymmetric transformations are a general and powerful approach for the construction of carbo- heterocyclic systems with one more stereocenters. In addition, newly developed multiple cascade reactions an attractive strategy increasing molecular complexity in step. recent years, great progress has been made this area use various palladium nickel complexes P- N-donor chiral ligands. This review highlights developments intramolecular Heck reactions, reductive types (intramolecular Heck/Heck, Heck/nucleophilic trapping, Heck/Tsuji-Trost, Heck/Suzuki-Miyaura, Heck/Sonogashira, Heck/carbonylation) synthesis complex molecules over past 5 years. A number examples from before 2016 included as background information. Particular attention is paid to inexpensive highly efficient catalysts considered here. perspective on current challenges potential future field type cyclizations also provided.

Language: Английский

Citations

55
Three-Component Visible-Light-Induced Palladium-Catalyzed 1,2-Alkyl Carbamoylation/Cyanation of Alkenes DOI
Xiangqing Jia, Ziyan Zhang, Vladimir Gevorgyan

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13217 - 13222

Published: Oct. 15, 2021

A mild visible-light-induced Pd-catalyzed one-pot three-component alkyl-carbamoylation and cyanation of alkenes was developed. This general transformation, which proceeds via the in situ formation a reactive ketenimine intermediate, allows for rapid construction broad range valuable amides nitriles from readily available alkenes, alkyl iodides, isocyanides. An efficient synthesis tetrazole amidine this approach also demonstrated.

Language: Английский

Citations

47
Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes DOI Creative Commons
Xianqing Wu, Aneta Turlik,

Baixue Luan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 12, 2022

Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed

Language: Английский

Citations

31