Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis DOI

Xian‐Wang Zeng,

Jia‐Ni Lin,

Wei Shu

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(23)

Опубликована: Апрель 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Язык: Английский

Asymmetric Cross-Coupling of Aldehydes with Diverse Carbonyl or Iminyl Compounds by Photoredox-Mediated Cobalt Catalysis DOI

Zhiyong Chi,

Jia-Bin Liao,

Xiuliang Cheng

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10857 - 10867

Опубликована: Апрель 8, 2024

The asymmetric cross-coupling of unsaturated bonds, hampered by their comparable polarity and reactivity, as well the scarcity efficient catalytic systems capable diastereo- enantiocontrol, presents a significant hurdle in organic synthesis. In this study, we introduce highly adaptable photochemical cobalt catalysis framework that facilitates chemo- stereoselective reductive cross-couplings between common aldehydes with broad array carbonyl iminyl compounds, including N-acylhydrazones, aryl ketones, aldehydes, α-keto esters. Our methodology hinges on synergistic mechanism driven photoredox-induced single-electron reduction subsequent radical–radical coupling, all precisely guided chiral catalyst. Various optically enriched β-amino alcohols unsymmetrical 1,2-diol derivatives (80 examples) have been synthesized good yields (up to 90% yield) high stereoselectivities >20:1 dr, 99% ee). Of particular note, approach accomplishes unattainable transformations disparate partners without reliance any external photosensitizer, thereby further emphasizing its versatility cost-efficiency.

Язык: Английский

Процитировано

18
Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis DOI

Xian‐Wang Zeng,

Jia‐Ni Lin,

Wei Shu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Язык: Английский

Процитировано

6
Titanium in photocatalytic organic transformations: current applications and future developments DOI
Jia‐Lin Tu, Binbin Huang

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(33), С. 6650 - 6664

Опубликована: Янв. 1, 2024

Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, unique reactivity organic synthesis. In the field of photocatalysis, titanium-based compounds such titanium dioxide (TiO

Язык: Английский

Процитировано

6
Functionalization of 1,3‐Butadiene Derivatives under Photo/Electrocatalysis DOI

Yinghui Huang,

Linhui Shen,

Chunhua Ma

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(28)

Опубликована: Май 20, 2024

Abstract In recent years, the functionalization of 1,3‐butadiene has become an attractive strategy for constructing allyl compounds with molecular and structural complexity, current research focuses on synthetic chemistry organic synthesis. Compared traditional synthesis method, methods promoted by photochemistry or electrochemistry represent environmentally friendly mild strategy. this review, reactions under photochemical/electrochemical processes in years are reviewed according to classification systems, particular emphasis corresponding reaction mechanism, which lays a foundation further exploration new catalytic methods.

Язык: Английский

Процитировано

5
Dual Photoredox- and Titanium Catalysis-Enabled Three-Component Radical Propargylation of Aldehydes with 1,3-Enynes DOI

Xuehan Qi,

Renxu Cao,

Zhixian Wu

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Herein, a straightforward and practical strategy involving radicals for the three-component carbonyl propargylation via dual photoredox titanium catalysis is presented. This delivers homopropargyl alcohols includes readily available starting materials, broad substrate scope, high functional group tolerance, mild reaction conditions. Catalytic Cp2TiCl2, recognized as an inexpensive, nontoxic, bench-stable source, employed.

Язык: Английский

Процитировано

0
Dialkylation of 1,3-Dienes with Aldehydes and Cyclopropanols toward Homoallylic Alcohols by Dual Photoredox and Chromium Catalysis DOI

Gaochen Xu,

Pei Guan,

Lu Deng

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 27, 2025

A visible-light-induced three-component coupling of aldehydes, 1,3-dienes, and cyclopropyl alcohols using dual photoredox chromium catalysis is herein described. This efficient protocol achieves the dialkylation 1,3-dienes toward 1,4-disubstituted homoallylic in moderate to good yields with excellent regioselectivity, featuring mild reaction conditions, functional group tolerance, gram-scale synthesis. Mechanistic study suggests that photoinduced sequential ring opening alcohol radical nucleophilic cascade addition are involved catalytic cycle.

Язык: Английский

Процитировано

0
Catalytic hydrofunctionalizations of alkenes via hydrogen atom transfer with 3d transition metal complexes (MHAT): A pragmatic approach to recent contributions DOI Creative Commons
Antonio Torres-Calis, Juventino J. Garcı́a

Applied Catalysis A General, Год журнала: 2025, Номер unknown, С. 120379 - 120379

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0
Photochemical Metal‐Hydride Hydrogen Atom Transfer Mediated Radical Hydrofunctionalization of Dienes and Allenes DOI

Huaipu Yan,

Jing‐Ran Shan, Lei Shi

и другие.

ChemCatChem, Год журнала: 2023, Номер 16(2)

Опубликована: Ноя. 17, 2023

The metal-hydride hydrogen atom transfer (MHAT) method is widely recognized as a powerful technique for functionalizing alkenes. However, its application in the functionalization of industrial feedstock dienes and allenes relatively rare due to challenges related chemo-selectivity. In recent studies, Co-porphines have been identified highly efficient catalysts under photoirradiation MHAT, demonstrating an exceptional level chemoselectivity allenes, while disregarding other simple olefins present. This novel enables selective reductive coupling pyridines with allylation aldehydes by combination Ti catalysis. Mechanistic studies density functional theory (DFT) calculations support idea that non-reversible atoms from cobalt hydride leading generation allyl radicals, key step catalytic cycle.

Язык: Английский

Процитировано

5
Formation of TEMPO Adducts with Hydrogen Atom Transfer: A New Pathway to Versatile Hydrofunctionalizations of Olefins DOI Creative Commons
Chengbo Yao, Muinat A. Aliyu, Jack R. Norton

и другие.

Опубликована: Фев. 12, 2024

Since the seminal work by Mukaiyama, many research groups reported hydrofunctionalization of olefin with different metal hydrides in situ. Despite rapid development MHAT (metal-catalyzed hydrogen atom transfer)-derived reactions, need for using catalyst systems to accommodate reactivities makes it not appealing. Here, we describe a two-step process access broad range olefins. The first step involves cobalt-catalyzed formation TEMPO adduct from reaction demonstrates substrate scope and functional group tolerance. second photocatalytic nucleophilic addition generate new C-C, C-N, C-O, C-F, C-Cl bond. Interestingly our methodology, fluorination could be achieved short time, showing its potential PET applications. Combining two steps, net olefins can simply changing nucleophiles step. Noteworthily, diastereoselective hydration was also demonstrated employing bulkiness TEMPO.

Язык: Английский

Процитировано

1
Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis DOI

Xian‐Wang Zeng,

Jia‐Ni Lin,

Wei Shu

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(23)

Опубликована: Апрель 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Язык: Английский

Процитировано

0