Asymmetric and switchable divergent multicomponent reactions involving distinct alkynes via palladium catalysis

Zhao, Zhengyang; Zheng, Jia-Le; Du, Wei; Chen, Ying‐Chun

doi:10.1016/j.checat.2022.09.014

Cited by 12 publications

(1 citation statement)

References 41 publications

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“…33 Besides being trapped by boronic acids, the key intermediates INT14 (Scheme 9c) also could undergo Sonogashira coupling with terminal alkynes 41 without other additives to provide enantioenriched tetrasubstituted alkenes 42 with good to excellent stereoselectivity (Scheme 10). 34 Sequential conversion to 2,5-dihydropyrroles 43 bearing an (E)-exocyclic double bond motif could be realized by Pd-(OAc) 2 -mediated syn-hydroamination. Interestingly, the construction of optically pure products 44 with a (Z)-exocyclic double bond could be directly accomplished by slightly tuning the catalytic conditions.…”

Section: Homo Activation Of Electron-neutral 13-enynes By Palladium(0)mentioning

confidence: 99%

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

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The development of a new catalytic strategy plays a vital role in modern organic chemistry since it permits bond formation in an unprecedented and more efficient manner. Although the application of preformed metal complexes as π-baseactivated reagents have enabled diverse transformations elegantly, the concept and strategy by directly utilizing transition metals as efficient π-Lewis base catalysts remain underdeveloped, especially in the field of asymmetric catalysis. Here, we outline our perspective on the discovery of palladium(0) as an efficient π-Lewis base catalyst, which is capable of increasing the highest occupied molecular orbital (HOMO) energy of both electron-neutral and electron-deficient 1,3-dienes and 1,3-enynes upon flexible η 2complexes formed in situ and resultant π-backdonation. Thus, fruitful carbon−carbon-forming reactions with diverse electrophiles can be achieved enantioselectively in a vinylogous addition pattern, which is conceptually different from the classical oxidative cyclization mechanism. Emphasis will be given to the concept and mechanism elucidation, catalytic features, and reaction design together with perspective on the further development of this emerging field.

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Section: Homo Activation Of Electron-neutral 13-enynes By Palladium(0)mentioning

confidence: 99%

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

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Rapid Construction of Hexahydro‐1H‐pyrrolo[3,2‐c]pyridines with Functionalized 1,3‐Enynes and Imines via Palladium Catalysis

Huang

Chen

et al. 2023

Asian J Org Chem

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Presented herein is a palladium catalyzed tandem reaction between 3‐aminoethyl group tethered 1,3‐enynes and imines, proceeding through a cascade vinylogous addition/reductive elimination/protonation/allylic amination and 1,3‐hydrogen transfer sequence. A collection of complex hexahydro‐1H‐pyrrolo[3,2‐c]pyridine architectures were straightforwardly constructed in moderate yields and diastereoselectivity.

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Nickel‐Catalyzed Unsymmetrical Bis‐Allylation of Alkynes

et al. 2023

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The catalytic bis‐allylation of alkynes is an important but challenging protocol to construct all‐carbon tetra‐substituted alkenes. Particularly, the catalytic unsymmetrical bis‐allylation of alkynes remains as an underexplored task to date. We herein report an unprecedented unsymmetrical bis‐allylation by simultaneously utilizing electrophilic trifluoromethyl alkene and nucleophilic allylboronate as the allylic reagents. With the aid of robust Ni0/NHC catalysis, valuable skipped trienes can be obtained in high regio‐ and stereo‐selectivities under mild conditions. Mechanistic studies indicate that the reaction may proceed through a β‐fluorine elimination of a nickelacycle followed by a transmetalation step with allylboronate. The present method exhibits a good tolerance of various functional groups. Besides, the skipped triene products can undergo an array of elaborate transformations, which highlights the potential applications of this strategy.

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Asymmetric and switchable divergent multicomponent reactions involving distinct alkynes via palladium catalysis

Cited by 12 publications

References 41 publications

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Rapid Construction of Hexahydro‐1H‐pyrrolo[3,2‐c]pyridines with Functionalized 1,3‐Enynes and Imines via Palladium Catalysis

Nickel‐Catalyzed Unsymmetrical Bis‐Allylation of Alkynes

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