Palladium(<scp>ii</scp>)-catalyzed enantioselective intermolecular oxidative diarylation of internal enamides

Xia, Tingting; Yang, Xi; Ding, Haojie; Zhang, Yetong; Fang, Ke; Wu, Xianqing; Qü, Jingping; Chen, Yifeng

doi:10.1039/d2cc03202c

Cited by 8 publications

(2 citation statements)

References 63 publications

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“…Following that, the same group [38] disclosed a Pd(II)-catalyzed, the remarkably enantioselective intermolecular oxidative 1,2-DIAR reaction of internal enamides with aryl boronic acids (Scheme 22). This groundbreaking advancement facilitates the efficient formation of two adjacent stereocenters, exhibiting exceptional diastereo-and enantioselectivities.…”

Section: Palladium Catalysismentioning

confidence: 99%

Recent Advances in the 1,2‐Diarylation of Alkenes

Jose,

Mathew

2023

Adv Synth Catal

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Alkenes are a fascinating functional class that can be converted into various structures. A desirable and durable synthetic method for forming two C−C bonds across an olefin is the dicarbofunctionalization of olefins, catalyzed by transition metals. This method enables a rapid expansion of molecular complexity in a single step. Among the myriad of efficient strategies for alkene difunctionalization, the 1,2‐diarylation mode stands out primarily due to its remarkable ability to incorporate two hindered aryl groups across the C=C bond in a versatile and straightforward manner. This review covers the recent advances in the 1,2‐diarylation of alkenes from 2018 to 2023, focusing on different transition metals employed as catalysts.

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Section: Palladium Catalysismentioning

confidence: 99%

Recent Advances in the 1,2‐Diarylation of Alkenes

Jose,

Mathew

2023

Adv Synth Catal

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“…Furthermore, The 1,2‐diarylation of electronically unactivated internal alkenes has met with formidable challenges because of low reactivity, reduced polarization, and competitive 1,n‐diarylation via undesired chain‐walking isomerization (Figure 1A‐c) [4f, 7, 8] . In contrast with the precedent strategy employing electronically stabilized allyl or benzyl metal species, [4g–l] achieving highly diastereo‐ and enantioselective 1,2‐diarylation of unactivated internal alkenes poses an additional challenge due to the related unstable chiral Heck C(sp 3 )‐metal intermediates [9] . Although several elegant examples for the diastereoselective intermolecular 1,2‐diarylation using unactivated internal alkenes have been explored, they required a specific ligand [6j–l] or suffered from poor diastereoselectivity (≈1 : 1 dr) [6m] .…”

Section: Introductionmentioning

confidence: 99%

Directed Asymmetric Nickel‐Catalyzed Reductive 1,2‐Diarylation of Electronically Unactivated Alkenes

Dong

Tang

et al. 2023

Angew Chem Int Ed

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Transition‐metal catalyzed intermolecular 1,2‐diarylation of electronically unactivated alkenes has emerged as an extensive research topic in organic synthesis. However, most examples are mainly limited to terminal alkenes. Furthermore, transition‐metal catalyzed asymmetric 1,2‐diarylation of unactivated alkenes still remains unsolved and is a formidable challenge. Herein, we describe a highly efficient directed nickel‐catalyzed reductive 1,2‐diarylation of unactivated internal alkenes with high diastereoselectivities. More importantly, our further effort towards enantioselective 1,2‐diarylation of the unactivated terminal and challenging internal alkenes is achieved, furnishing various polyarylalkanes featuring benzylic stereocenters in high yields and with good to high enantioselectivities and high diastereoselectivities. Interestingly, the generation of cationic Ni‐catalyst by adding alkali metal fluoride is the key to increased efficiency of this enantioselective reaction.

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Enantioselective Aminosilylation of Alkenes by Palladium/Ming‐Phos‐Catalyzed Tandem Narasaka–Heck/Silylation Reaction

Cao,

Han,

et al. 2024

Advanced Science

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A Pd‐catalyzed enantioselective aminosilylation of alkenes via tandem Aza‐Heck/silylation reaction under Pd/Sadphos catalysis is disclosed. A wide array of oxime esters and silicon reagents are tolerated, furnishing the chiral pyrrolines bearing one quaternary or two contiguous stereocenters in good yield with high enantioselectivity. Not only terminal alkenes but also tri‐substituented internal alkenes successfully participate in the reaction, delivering vicinal stereocenters in complete diastereoselectivity and high enantioselectivity. DFT study is conducted to probe the reaction pathway and the origin of the enantioselectivity, which revealed that the stereoinduction arises from the weak interaction between the aromatic ring of the substrate fragment and naphthyl group in the ligand.

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Palladium(ii)-catalyzed enantioselective intermolecular oxidative diarylation of internal enamides

Abstract: The construction of vicinal stereogenic centers via the simultaneous formation of two C-C bonds across alkenes under oxidative conditions is a stubborn challenge. Herein, we report a Pd(II)-catalyzed highly enantioselective...

Cited by 8 publications

References 63 publications

Recent Advances in the 1,2‐Diarylation of Alkenes

Recent Advances in the 1,2‐Diarylation of Alkenes

Directed Asymmetric Nickel‐Catalyzed Reductive 1,2‐Diarylation of Electronically Unactivated Alkenes

Enantioselective Aminosilylation of Alkenes by Palladium/Ming‐Phos‐Catalyzed Tandem Narasaka–Heck/Silylation Reaction

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