Rhodium Catalyzed Regioselective C−H Allylation of Simple Arenes via C−C Bond Activation of <i>Gem</i>‐difluorinated Cyclopropanes

Jiang, Zhong‐Tao; Huang, Jiangkun; Zeng, Yaxin; Hu, Fangdong; Xia, Ying

doi:10.1002/anie.202016258

Cited by 77 publications

(41 citation statements)

References 78 publications

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“…On the basis of this hypothesis, as well as our research experiences on rhodium-catalyzed C-C activations, 24 we proceeded with this project, using catalysis by rhodium complexes. 25…”

Section: Synpacts Synlettmentioning

confidence: 99%

Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates

Jiang¹,

Zeng²,

Xia³

2021

Synlett

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Gem-difluorinated cyclopropanes have become an important type of allyl surrogates through transition-metal catalyzed ring-opening process, which has been demonstrated recently by various important advances especially via palladium catalysis. The versatile fluorinated allyl species generated in this way from gem-difluorinated cyclopropanes exhibit unique advantages comparing with traditional allyl sources. By using gem-difluorinated cyclopropanes as allyl surrogates, we achieved direct allylation of simple arenes via rhodium catalysis under mild conditions. This transformation enables directing-group free allylation of simple arenes including electron-neutral, -rich and -deficient ones. Herein we will give a brief introduction of this area and discuss how we thought and designed in our recent work. 1 Introduction 2 Our Design 3 Condition Optimization and Substrate Scope 4 Synthetic Applications 5 Mechanistic Discussions 6 Conclusion and Outlook

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“…On the basis of this hypothesis, as well as our research experiences on rhodium-catalyzed C-C activations, 24 we proceeded with this project, using catalysis by rhodium complexes. 25…”

Section: Synpacts Synlettmentioning

confidence: 99%

Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates

Jiang¹,

Zeng²,

Xia³

2021

Synlett

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“…In 2021, we disclosed a rhodium-catalyzed cross-coupling reaction between gem-difluorinated cyclopropanes with simple arenes (Scheme 18). 30 The arene C−H allylation products were obtained in high yields and excellent regioselectivity under the catalytic system of [Rh(CO)2Cl]2/rac-BINAP/AgBF4.…”

Section: Scheme 17 Cobalt-catalyzed Fluoroallylation Of Aldehydesmentioning

confidence: 98%

Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes

Zhu¹,

Zeng²,

Jiang³

et al. 2022

Synlett

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As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties due to the gem-difluoro substitution, and thus their reactions have received much attention from the synthetic community. Recently, gem-difluorinated cyclopropanes have gradually emerged as a type of novel and unique fluorinated allylic synthon in cross-coupling reactions for the synthesis of monofluoroalkenes. Here, we briefly summarize recent advances on transition-metal catalyzed reactions of gem-difluorinated cyclopropanes. 1. Introduction 2. Palladium catalyzed reactions with linear selectivity 3. Palladium catalyzed reactions with branched selectivity 4. Other metal catalyzed reactions 5. Conclusions

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“…This strategy was further extended to prepare an array of appealing β‐fluoroalkene structures integrated with C−C, C−N or C−S bond formations [9] . Very recently, Xia and co‐workers reported an elegant Rh‐catalyzed C−H allylation of arenes with gem ‐difluorocyclopropanes [10] . Mechanistically, those external nucleophiles (whether interact with the metal center or not) preferentially attack at the sterically less hindered C1 atom, and the linear fluorinated allylic scaffolds (β‐fluoroalkenes) were obtained predominantly (Scheme 1 c, left) via the π‐coordination.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Defluorinative Alkylation of gem‐Difluorocyclopropanes: Switching Regioselectivity via Simple Hydrazones

2021

Angewandte Chemie

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Conventional approaches for Pd-catalyzed ringopening cross-couplings of gem-difluorocyclopropanes with nucleophiles predominantly deliver the b-fluoroalkene scaffolds (linear selectivity). Herein, we report ac ooperative strategy that can completely switch the reaction selectivity to give the alkylated a-fluoroalkene skeletons (branched selectivity). The unique reactivity of hydrazones that enables analogous inner-sphere 3,3'-reductive elimination driven by denitrogenation, as well as the assistance of steric-embedded Nheterocyclic carbene ligand, are the key to switch the regioselectivity.Awide range of hydrazones derived from naturally abundant aryl and alkyla ldehydes are well applicable,a nd various gem-difluorocyclopropanes,i ncluding modified pharmaceutical and biological molecules,c an be efficiently functionalized with high value alkylated a-fluorinated alkene motifs under mild conditions. Scheme 1. Functionalization of gem-difluorocyclopropanes to synthesize mono-fluorinated alkene scaffolds and the strategy to switch the regioselectivity.

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Rhodium Catalyzed Regioselective C−H Allylation of Simple Arenes via C−C Bond Activation of Gem‐difluorinated Cyclopropanes

Cited by 77 publications

References 78 publications

Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates

Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates

Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes

Palladium‐Catalyzed Defluorinative Alkylation of gem‐Difluorocyclopropanes: Switching Regioselectivity via Simple Hydrazones

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