Palladium‐Catalysed Decarboxylative Generation and Regiodivergent Prenylation of 2‐Azaallyl Anions

Wang, Xiaoqian; Zeng, Xi; Lin, Qiao; Li, Minyan; Walsh, Patrick J.; Chruma, Jason J.

doi:10.1002/adsc.201900491

Cited by 14 publications

(2 citation statements)

References 49 publications

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“…Economical methods to prepare homoallylic amines remain in demand. The use of allylic alkylations [49][50][51][52][53][54][55][56] or decarboxylative allylic alkylation reactions [56][57][58][59][60][61] to prepare homoallylic amines has been demonstrated with various transition-metal catalysts, including Ni, Pd, Cu, Zn, Ir, Rh, and Yb (Fig. 1a, b).…”

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confidence: 99%

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

et al. 2021

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Allylation of nucleophiles with highly reactive electrophiles like allyl halides can be conducted without metal catalysts. Less reactive electrophiles, such as allyl esters and carbonates, usually require a transition metal catalyst to facilitate the allylation. Herein, we report a unique transition-metal-free allylation strategy with allyl ether electrophiles. Reaction of a host of allyl ethers with 2-azaallyl anions delivers valuable homoallylic amine derivatives (up to 92%), which are significant in the pharmaceutical industry. Interestingly, no deprotonative isomerization or cyclization of the products were observed. The potential synthetic utility and ease of operation is demonstrated by a gram scale telescoped preparation of a homoallylic amine. In addition, mechanistic studies provide insight into these C(sp3)–C(sp3) bond-forming reactions.

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confidence: 99%

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

et al. 2021

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“…The catalytic C-H functionalization of heterocycles [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] is a straightforward and economic route to achieve post-modification of drugs and active molecules. And the introduction of dimethylallyl-related units (C5 skeletons) [71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88] into functional molecules often leads to dramatic changes in their lipophilicities and metabolic stabilities. Recently, our group developed a Pd-catalyzed chemoselective coupling of oxindoles with isoprene [89].…”

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confidence: 99%

Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene

Zhang

Wang

et al. 2023

Chinese Journal of Catalysis

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Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Jiang

Zhang

et al. 2021

Angewandte Chemie

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Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in areaction that involves multiple active sites.H erein, an orthogonal regulation of nucleophilic and electrophilic sites in the regiodivergent hydroamination of isoprene with indazoles is demonstrated. Under Pd-hydride catalysis,t he 1,2-or 4,3insertion pathway with respect to the electrophilic sites on isoprene could be controlled by the choice of ligands.Interms of the nucleophilic sites on indazoles,t he reaction occurs at either the N 1-o rN 2-position of indazoles is governed by the acid co-catalysts.P reliminary experimental studies have been performed to rationalizet he mechanism and regioselectivity. This study not only contributes ap ractical tool for selective functionalization of isoprene,b ut also provides ag uide to manipulate the regioselectivity for the N-functionalization of indazoles.

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Palladium‐Catalysed Decarboxylative Generation and Regiodivergent Prenylation of 2‐Azaallyl Anions

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 14 publications

References 49 publications

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

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