Asymmetric formal sp2-hydrocarbonations of dienes and alkynes via palladium hydride catalysis DOI Creative Commons

Ming-Qiao Tang,

Zijiang Yang, Zhi‐Tao He

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 9, 2023

Abstract Transition metal-catalyzed asymmetric hydrofunctionalizations of unsaturated bonds via π-ƞ 3 substitution have emerged as a reliable method to construct stereogenic centers, and mainly rely on the use heteroatom-based or carbon nucleophiles bearing acidic C-H bonds. In comparison, sp 2 are generally not under consideration because enormous challenges in cleaving corresponding inert Here, we report protocol achieve formal hydrocarbonations, including hydroalkenylation, hydroallenylation hydroketenimination both 1,3-dienes alkynes hydroalkylation Wittig reaction cascade. A series unachievable motifs hydrofunctionalizations, such di-, tri- tetra-substituted alkenes, allenes, tri-substituted ketenimines allyl skeletons all facilely constructed high regio-, diastereo- enantioselectivities with this cascade design. Stereodivergent synthesis four stereoisomers 1,4-diene stereocenter Z/E-controllable olefin unit highlights power present protocol. An interesting mechanistic feature is revealed that alkyne actually undergoes hydrocarbonation formation conjugated diene intermediate, different from conventional viewpoint hydrofunctionalization only involves allene species.

Язык: Английский

Theoretical investigation on cobalt-catalyzed hydroacylation reaction: Mechanism and origin of stereoselectivity DOI
Yang Wang, Han Zhang, Yue Liu

и другие.

Molecular Catalysis, Год журнала: 2022, Номер 527, С. 112410 - 112410

Опубликована: Июнь 7, 2022

Язык: Английский

Процитировано

23

Chemodivergent, Regio‐ and Enantioselective Cycloaddition Reactions between 1,3‐Dienes and Alkynes DOI Creative Commons
Dipshi Singh, T. V. RajanBabu

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(8)

Опубликована: Дек. 15, 2022

Alkynes and 1,3-dienes are among the most readily available precursors for organic synthesis. We report two distinctly different, catalyst-dependent, modes of regio- enantioselective cycloaddition reactions between these classes compounds providing rapid access to highly functionalized 1,4-cyclohexadienes or cyclobutenes from same precursors. Complexes an earth abundant metal, cobalt, with several commercially chiral bisphosphine ligands narrow bite angles catalyze [4+2]-cycloadditions a 1,3-diene alkyne giving cyclohexa-1,4-diene in excellent chemo-, enantioselectivities. In sharp contrast, complex finely tuned phosphino-oxazoline ligand promotes unique [2+2]-cycloaddition terminal double bond diene cyclobutene

Язык: Английский

Процитировано

22

Mechanism and Origins of Enantioselectivity of Cobalt-Catalyzed Intermolecular Hydroarylation/Cyclization of 1,6-Enynes with N-Pyridylindoles DOI

Deping Kong,

Hongli Wu,

Jiaao Ge

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(9), С. 6438 - 6443

Опубликована: Апрель 11, 2022

Density functional theory calculations were performed to investigate the cobalt-catalyzed intermolecular hydroarylation/cyclization of 1,6-enynes with N-pyridylindoles. The computations reveal that reaction begins oxidative cyclization 1,6-enyne afford five-membered cobaltacycle, from which metal-assisted σ-bond metathesis/C-C reductive elimination led final product. initial constitutes rate-determining step overall reaction. steric repulsion and π···π interaction found play a crucial role in dictating experimentally observed enantioselectivity.

Язык: Английский

Процитировано

20

Copper-Catalyzed Carbonylation Reactions: A Personal Account DOI
Xiao‐Feng Wu, Hui‐Qing Geng

Synthesis, Год журнала: 2024, Номер 56(17), С. 2595 - 2613

Опубликована: Янв. 9, 2024

Abstract Carbonylation reactions have been widely used to construct carbonyl-containing molecules or carbon enhancement reactions, which are mostly catalyzed by noble metals (Pd, Rh, Ru, Ir). In this review, we introduce the copper-catalyzed carbonylation that developed in our group. Diverse using various substrates, including of C–H activated alkanes, difunctionalization unsaturated C–C bonds, and alkyl halides via radical pathway. 1 Introduction 2 Cu-Catalyzed C(sp 3)–H Bonds 3 Carbonylative Difunctionalization Unsaturated 4 Cu–X (H B) Mediated Acylation with Electrophiles 5 6 Alkyl Halides 7 Other Types Copper-Catalyzed Reactions 8 Conclusion Outlook

Язык: Английский

Процитировано

5

Asymmetric formal sp2-hydrocarbonations of dienes and alkynes via palladium hydride catalysis DOI Creative Commons

Ming-Qiao Tang,

Zijiang Yang, Zhi‐Tao He

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 9, 2023

Abstract Transition metal-catalyzed asymmetric hydrofunctionalizations of unsaturated bonds via π-ƞ 3 substitution have emerged as a reliable method to construct stereogenic centers, and mainly rely on the use heteroatom-based or carbon nucleophiles bearing acidic C-H bonds. In comparison, sp 2 are generally not under consideration because enormous challenges in cleaving corresponding inert Here, we report protocol achieve formal hydrocarbonations, including hydroalkenylation, hydroallenylation hydroketenimination both 1,3-dienes alkynes hydroalkylation Wittig reaction cascade. A series unachievable motifs hydrofunctionalizations, such di-, tri- tetra-substituted alkenes, allenes, tri-substituted ketenimines allyl skeletons all facilely constructed high regio-, diastereo- enantioselectivities with this cascade design. Stereodivergent synthesis four stereoisomers 1,4-diene stereocenter Z/E-controllable olefin unit highlights power present protocol. An interesting mechanistic feature is revealed that alkyne actually undergoes hydrocarbonation formation conjugated diene intermediate, different from conventional viewpoint hydrofunctionalization only involves allene species.

Язык: Английский

Процитировано

11