Enantioselective Heck/Tsuji−Trost Reaction of Flexible Vinylic Halides with 1,3-Dienes DOI Creative Commons
Junliang Zhang, Li‐Zhi Zhang, Peichao Zhang

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Авг. 16, 2024

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient tandem Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. A variety functional cyclic isoprenoids, which are key structural motifs numerous natural products family, were delivered good yields excellent regio-, diastereo- enantioselectivity. Specifically, Heck insertion stereodetermining step to form ƞ3 π-allyl complex situ trapping nucleophiles enable Heck/etherification formal (4+2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands vital component achieving catalytic reactivity This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Язык: Английский

Enantioselective Construction of Tetrahydroindole Skeletons by Rh‐Catalyzed [2+2+2] Cycloaddition of Homopropargyl Enamides with Alkynes DOI Creative Commons

Kairi Yamashiro,

Kohei Fujii, Yu Sato

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(38)

Опубликована: Июнь 26, 2024

We have developed the Rh-catalyzed enantioselective [2+2+2] cycloaddition of homopropargyl enamides (tosylamide-tethered 1,6-enynes) with alkynes to construct tetrahydroindole skeletons found in natural alkaloids and pharmaceuticals. This proceeds at room temperature high yields regio- enantioselectivity a broad substrate scope. The preparative scale reaction followed by substituent conversion on nitrogen atom diastereoselective [4+2] singlet O

Язык: Английский

Процитировано

2
Synthetic Approaches to α‐, β‐, γ‐, and δ‐Lycoranes DOI
Diego Díaz Bautista, Miguel A. Vilchis‐Reyes,

Ever A. Blé González

и другие.

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(35)

Опубликована: Июль 11, 2023

Lycorane is a pentacyclic core presented in alkaloids isolated from the

Язык: Английский

Процитировано

5
Asymmetric 1,n‐Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis** DOI

Xintuo Yang,

Pinhong Chen, Guosheng Liu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 18, 2024

A palladium-catalyzed asymmetric 1,n-remote aminoacetoxylation of cis-alkenes has been developed using PhI(OAc)

Язык: Английский

Процитировано

1
Asymmetric 1,n‐Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis** DOI

Xintuo Yang,

Pinhong Chen, Guosheng Liu

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(35)

Опубликована: Май 18, 2024

Abstract A palladium‐catalyzed asymmetric 1,n‐remote aminoacetoxylation of cis ‐alkenes has been developed using PhI(OAc) 2 as an oxidant, providing the acetoxylated lactams with excellent enantioselectivities under mild reaction conditions. The sterically hindered pyridine‐oxazoline (Pyox) L3 a tert ‐butyl group in oxazoline ring and propyl C6 position pyridinyl is vital for reaction, where former good aminopalladation step latter chain walking process. enantioenriched lactam products were proven to be building blocks synthesis azabicycles.

Язык: Английский

Процитировано

1
Theoretical insight into the activity and selectivity in palladium/Ming-Phos-catalyzed three-component asymmetric synthesis of gem-diarylmethine silanes DOI
Bo-Wen Xiao, Tian‐Yu Sun, Junliang Zhang

и другие.

Science China Chemistry, Год журнала: 2023, Номер 66(10), С. 2817 - 2827

Опубликована: Сен. 7, 2023

Язык: Английский

Процитировано

2
DFT Studies on Pd/Xiao‐Phos‐Catalyzed Asymmetric Arylation of Secondary Phosphine Oxides DOI
Si‐Yuan Liu, Zhiming Li, Hao Guo

и другие.

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(44)

Опубликована: Окт. 24, 2023

Abstract Asymmetric arylation of secondary phosphine oxides (SPOs) has been rapidly developed, while there are few theoretical studies reported. DFT computations were carried out to study the whole catalytic cycle Pd/Xiao‐Phos‐catalyzed asymmetric SPOs, and a modified mechanism including tautomerization was presented. Some new mechanisms have traversed, base‐assisted tautomerization. These different from existing report, where is most favored. The resulting intermediate enters downstream directly. Furthermore, oxidative addition identified as enantioselectivity‐determining step. IGMH analysis results indicate that non‐bonding interactions between Xiao‐Phos SPO parts determine enantioselectivity. This work not only provides deeper insights into self‐adaptive property SadPhos ligands but also offers valuable guidance for ligand design. Newly proposed will bring some inspiration subsequent related research.

Язык: Английский

Процитировано

2
Olefin Difunctionalization With Two Different Atoms: 1,2-Carboamination of Olefins DOI
Junfeng Yang, Junliang Zhang

Elsevier eBooks, Год журнала: 2023, Номер unknown, С. 329 - 349

Опубликована: Июнь 2, 2023

Язык: Английский

Процитировано

1
Origin of Enantio- and Chemoselectivity in the Synthesis of Spirocycles via Palladium/Xu-Phos-Catalyzed Cascade Heck/Remote C(sp2)–H Alkylation: A Computational Mechanistic Study DOI
Xuexiang Ma, Aili Feng, Dongju Zhang

и другие.

The Journal of Physical Chemistry A, Год журнала: 2023, Номер 127(42), С. 8882 - 8891

Опубликована: Окт. 13, 2023

Density functional theory (DFT) calculations were performed to study the mechanism and factors affecting enantio-, regio-, chemoselectivities in palladium/Xu-Phos-catalyzed cascade Heck/remote C(sp2)-H alkylation reaction. The active catalyst is found be able sustain coordination with P S atoms can adapt its mode accommodate significant steric hindrance between ligand substrate, unlike previous findings that showed O atoms. reaction established occur sequence through oxidative addition of aryl iodide Pd(0), intramolecular alkene insertion, bond activation, C(sp2)-C(sp3) reductive elimination. elimination identified as rate-determining step, insertion enantioselectivity-determining step. high enantioselectivity originates from stronger electronic interaction substrate; exclusive 5-exo-regioselectivity due nucleophilicity terminal carbon atom, chemoselectivity C-H activation over carboiodination driven by thermodynamics.

Язык: Английский

Процитировано

1
Synergistic Palladium/Copper‐Catalyzed 1,4‐Difunctionalization of 1,3‐Dienes for Stereodivergent Construction of 1,5‐Nonadjacent Stereocenters DOI
Hongfa Wang, Ruiyuan Zhang, Weiwei Zi

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(21)

Опубликована: Март 21, 2024

Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.

Язык: Английский

Процитировано

0
Stereodivergent Construction of 1,5/1,7‐Nonadjacent Tetrasubstituted Stereocenters Enabled by Pd/Cu‐Cocatalyzed Asymmetric Heck Cascade Reaction DOI
Panpan Li,

Zijiao Liu,

Xiaohong Huo

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(35)

Опубликована: Май 16, 2024

Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.

Язык: Английский

Процитировано

0