Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

Li, Wanfang; Boon, Jie Kang; Zhao, Yu

doi:10.1039/c7sc03149a

Cited by 207 publications

(98 citation statements)

References 62 publications

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“…In this context, very recently, Zhao et al. reported nickel‐catalyzed 1,3 difunctionalization of allylamine moieties …”

Section: Methodsmentioning

confidence: 99%

“…[5] In this context, very recently,Z hao et al reported nickel-catalyzed 1,3 difunctionalization of allylamine moieties. [6] N-Containingc ompounds such as imides [7] and triazole [8] moieties are presenti navarietyo fb iologically and medicinally active compounds, and their synthesis and functionalization have received great attention. Traditionally,t he synthesis of imides have relied primarily on amides with carbonyl chlorides, aldehydes, and acetic anhydride.…”

mentioning

confidence: 99%

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Copper‐Catalyzed Oxidative C−H Bond Functionalization of N‐Allylbenzamide for Regioselective C−N and C−O Bond Formation

Ranjith

Krishna

2019

Chemistry An Asian Journal

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Copper‐catalyzed oxidative couplings of N‐allylbenzamides for C−N and C−O bond formations have been developed through C−H bond functionalization. To demonstrate the utility of this approach, it was applied to the synthesis of β‐aminoimides and imides. To the best of our knowledge, these are the first examples in which different classes of N‐containing compounds have been directly prepared from the readily available N‐allylbenzamides using an inexpensive catalyst/oxidant/base (CuSO4/TBHP/Cs2CO3) system.

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“…In this context, very recently, Zhao et al. reported nickel‐catalyzed 1,3 difunctionalization of allylamine moieties …”

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Copper‐Catalyzed Oxidative C−H Bond Functionalization of N‐Allylbenzamide for Regioselective C−N and C−O Bond Formation

Ranjith

Krishna

2019

Chemistry An Asian Journal

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“…The pyridine-directed 1,2-diarylation of vinylsilanes with aryl iodides and arylzincs was also achieved through nickel catalysis by the same group. [47] Very recently,apyrimidyl group-directed difunctionalizationo fa liphatic terminal alkenes with arylborons and organohalides was developed by Zhao et al [48] The regioselectivity was highly dependent on the electrophiles. When alkenyl bromides were used, 1,2-alkenylcarbonation took place selectively,w hereas 2,1-alkynylarylation was preferred with alkynyl halides.…”

Section: Nickel Catalysismentioning

confidence: 99%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

232

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Three-component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition-metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom- and step-economic efficiency. This Focus Review highlights recent advances in this field.

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“…The first one is the employment of 2,2‐disubstituted olefins or geometrically strained olefins, in which the β‐H atom is either absent in the generated C(sp 3 )‐[M] intermediates or hindered to undergo β‐H elimination . Alternatively, for olefins containing an appropriate directing group, a transient C(sp 3 )‐metallacycles might be formed to suppress the β‐H elimination . Apart from the substrate‐dependent strategy, some recently developed first‐row late transition‐metal catalysts demonstrate superior performance in catalyzing dicarbofunctionalization of unactivated olefins with β‐H atom in the generated C(sp 3 )‐[M] intermediates .…”

Section: Introductionmentioning

confidence: 99%

“…Regardless of substantial progress in the past two decades, regioselective dicarbofunctionalization still remains a challenge. In particular, Zhao and co‐workers investigated a Ni‐catalyzed dicarbofunctionalization of allyl moiety of N‐allylpyrimidin‐2‐amine ( 1 ) with organohalides ( 2 ) and organic boronic acids ( 3 ), where challenging regioselectivities were obtained based on the nature of halides. Interestingly, when aryl iodides are utilized for the dicarbofunctionalization of 1 , an intriguing 1,3‐regioselectivity is achieved (Scheme ‐I).…”

Section: Introductionmentioning

confidence: 99%

Computational Insights into the Divergent Regioselectivities for Nickel‐Catalyzed Dicarbofunctionalization of Allyl Moiety of N‐Allyl‐2‐aminopyrimidine

Wang

Bao

et al. 2020

Asian J Org Chem

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Herein, the origins of organohalide-dependent regioselectivities for Ni-catalyzed dicarbofunctionalization of allyl moiety of N-allyl-2-aminopyrimidine were explored by computational studies. When aryl iodides are used for the dicarbofunctionalization, the detailed reaction mechanistic pathway follows the sequential oxidative addition (OA), migratory insertion (MI), β-H elimination, H-migration, transmetalation, and reductive elimination (RE) to afford the 1,3dicarbofunctionalization products. Due to the presence of chelation of the pyrimidinyl moiety of substrate with Ni, the competitive β-H elimination leading to the product of Heck reaction is less favourable and thus the regioselective β-H elimination occurs. The formation of thermodynamically more stable intermediate is the driving force for the subsequent H-migration. When alkenyl bromides are used, alternative regioselectivity to give 1,2-dicarbofunctionalization products is obtained and the proposed mechanistic pathway proceeds sequentially via OA, MI, transmetalation, and RE. The main reason accounting for the different regioselectivity between aryl iodides and alkenyl bromides involved in dicarbofunctionalization is revealed. In addition, the reversed 2,1-regioselectivity achieved by using alkynyl halides in the Ni-catalyzed dicarbofunctionalization is via sequential steps of OA, transmetalation, MI, and RE. The mechanistic difference that the migratory insertion step is unlikely to occur after OA, which is in contrast to the other two mechanistic pathways, is rationalized.

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Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

Abstract: We present herein a nickel-catalyzed dicarbofunctionalization of alkenes using readily available organoboronic acids and organic halides in a three-component fashion.

Cited by 207 publications

References 62 publications

Copper‐Catalyzed Oxidative C−H Bond Functionalization of N‐Allylbenzamide for Regioselective C−N and C−O Bond Formation

Copper‐Catalyzed Oxidative C−H Bond Functionalization of N‐Allylbenzamide for Regioselective C−N and C−O Bond Formation

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Computational Insights into the Divergent Regioselectivities for Nickel‐Catalyzed Dicarbofunctionalization of Allyl Moiety of N‐Allyl‐2‐aminopyrimidine

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