Rhodium(<scp>iii</scp>)-catalyzed regioselective C2-alkenylation of indoles with CF<sub>3</sub>-imidoyl sulfoxonium ylides to give multi-functionalized enamines using a migratable directing group

Yang, Zhen; Tang, Jianhua; Li, Chen; Chen, Zhengkai; Wu, Xiao‐Feng

doi:10.1039/d2cc06127a

Cited by 17 publications

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References 64 publications

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“…Very recently, Wu, Chen and co-workers reported a rhodium( iii )-catalyzed regioselective C2-alkenylation of indoles using TFISYs as masked alkenylating agents for the preparation of indolyl- and trifluoromethyl-decorated enamine derivatives (Scheme 48). 61 The pyrimidyl group was applied as a migratable directing group to enable the reaction, whereas the pyridinyl was not a viable directing group. The transformation involved a Rh-catalyzed directed C–H functionalizations and a directing group migration cascade, producing the multi-functionalized enamine compounds in moderate to good yields.…”

Section: Synthesis Of Cf3-containing Heterocycles From Cf3-imidoyl Su...mentioning

confidence: 99%

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

et al. 2023

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Section: Synthesis Of Cf3-containing Heterocycles From Cf3-imidoyl Su...mentioning

confidence: 99%

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

et al. 2023

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“…Sulfoxonium ylides have experienced significant growth in organic synthesis . Imidoyl sulfoxonium ylides are particularly popular as metal carbene precursors (Scheme a). , In addition, imidoyl sulfoxonium ylides also have chameleonic reactivities: they react with various nucleophiles and electrophiles (Scheme b). These methods were powerful in constructing N -heterocycles, such as pyrroles and pyridines (Scheme b).…”

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Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Xu,

Yang,

2024

Org. Lett.

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We have found a chameleonic reactivity of imidoyl sulfoxonium ylides. On the one hand, imidoyl sulfoxonium ylides react with electron-deficient reagents, such as alkynyl esters, to lead to the formation of 1,2-dihydro-pyridines. The methyl group attached to the sulfur atom acts as a methylene donor. On the other hand, imidoyl sulfoxonium ylides react with pyridinium 1,4-zwitterionic thiolates, which leads to the formation of functionalized pyrroles. Both transformations feature mild reaction conditions and good functional group tolerance.S ulfoxonium ylides have experienced significant growth in organic synthesis. 1 Imidoyl sulfoxonium ylides are particularly popular as metal carbene precursors (Scheme 1a). 2,3 In addition, imidoyl sulfoxonium ylides also have chameleonic reactivities: 1 they react with various nucleophiles 4 and electrophiles 5 (Scheme 1b). These methods were powerful in constructing N-heterocycles, such as pyrroles and pyridines (Scheme 1b).We envision that imidoyl sulfoxonium ylides may have more chameleonic reactivity. 1 The methyl group (CH 3 -) connected to the sulfur atom could act as a methylene (CH 2 ) donor under suitable conditions (Scheme 1c). More specifically, when imidoyl sulfoxonium ylides react with a highly electrondeficient reagent, such as alkynyl esters, the methyl group attached to the sulfur atom acts as a methylene donor; this type of reactivity is very unusual. In addition, the electrondeficient alkynyl esters could react with pyridine and elementary sulfur to generate the pyridinium 1,4-zwitterionic thiolates. 6 These zwitterionic thiolates are nucleophilic; they may also react with imidoyl sulfoxonium ylides (Scheme 1c). 7 Herein, we report a chameleonic reactivity of imidoyl sulfoxonium ylides. This protocol offered access to synthetically important pyrroles and 1,2-dihydro-pyridines (Scheme 1c). Moreover, functionalized N-heterocycles, such as pyrroles and dihydro-pyridines, are ubiquitous in natural products, medicines, agrochemicals, and advanced materials. 8 We began our research by employing the reaction of CF 3imidoyl sulfoxonium ylides (TFISY) 1a and pyridinium 1,4zwitterionic thiolates 2 as the model system (Table 1). TFISYs could be easily prepared by the reaction of fluorinated

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“…As a C5 synthon, the [5 + 1] annulation of TFISYs with isothiocyanates or difluorocarbene/amines readily produce 2-trifluoromethyl quinolines . TFISYs could also be employed as a kind of highly reactive carbene precursors in numerous transition-metal-catalyzed C–H activation reactions . Among several application scenarios, the exploration of strategies using TFISYs as C5 synthons is far from being exhaustive and deserves more attention.…”

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Divergent Synthesis of Trifluoromethyl-Substituted 1,2-Dihydroquinoxalines and Diimines by Cascade Reactions of CF₃–Imidoyl Sulfoxonium Ylides with Azo Compounds

Wei,

Zheng,

et al. 2023

Org. Lett.

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Rhodium(iii)-catalyzed regioselective C2-alkenylation of indoles with CF₃-imidoyl sulfoxonium ylides to give multi-functionalized enamines using a migratable directing group

Abstract: A rhodium(III)-catalyzed regioselective C2-alkenylation of indoles for the construction of α-CF3 substituted enamines has been developed, which utilizes CF3-imidoyl sulfoxonium ylides (TFISYs) as alkenylating agents for the first time. A...

Cited by 17 publications

References 64 publications

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Divergent Synthesis of Trifluoromethyl-Substituted 1,2-Dihydroquinoxalines and Diimines by Cascade Reactions of CF₃–Imidoyl Sulfoxonium Ylides with Azo Compounds

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Rhodium(iii)-catalyzed regioselective C2-alkenylation of indoles with CF3-imidoyl sulfoxonium ylides to give multi-functionalized enamines using a migratable directing group

Abstract: A rhodium(III)-catalyzed regioselective C2-alkenylation of indoles for the construction of α-CF3 substituted enamines has been developed, which utilizes CF3-imidoyl sulfoxonium ylides (TFISYs) as alkenylating agents for the first time. A...

Cited by 17 publications

References 64 publications

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives

Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Divergent Synthesis of Trifluoromethyl-Substituted 1,2-Dihydroquinoxalines and Diimines by Cascade Reactions of CF3–Imidoyl Sulfoxonium Ylides with Azo Compounds

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Rhodium(iii)-catalyzed regioselective C2-alkenylation of indoles with CF₃-imidoyl sulfoxonium ylides to give multi-functionalized enamines using a migratable directing group

Divergent Synthesis of Trifluoromethyl-Substituted 1,2-Dihydroquinoxalines and Diimines by Cascade Reactions of CF₃–Imidoyl Sulfoxonium Ylides with Azo Compounds