Additive-Controlled Divergent Synthesis of Tetrasubstituted 1,3-Enynes and Alkynylated 3<i>H</i>-Pyrrolo[1,2-<i>a</i>]indol-3-ones via Rhodium Catalysis

Zhao, Fei; Gong, Xiaolan; Lu, Yudong; Jin, Qiao; Jia, Xiuwen; Ni, Hangcheng; Wu, Xiaowei; Zhang, Xiaoning

doi:10.1021/acs.orglett.0c03950

Cited by 49 publications

(25 citation statements)

References 134 publications

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“…However, directing group‐assisted coupling cyclization of indoles with 1,3‐diyne precursors have remain unexplored. Very recently, a remarkable example by Zhang and co‐workers showed that an Rh(III) catalyzed synthesis of tetrasubstituted 1,3‐enynes and alkylated 3 H ‐pyrrolo[1,2‐ a ]indol‐3‐ones derivatives from indoles and 1,3‐diynes (Scheme 1c) [17] . However, the methodology showed a limited scope of dialkynes and most of the products derived with alkyl substituted 1,3‐diyne precursors.…”

Section: Methodsmentioning

confidence: 99%

Rh(III)‐Catalyzed [3+2] Annulation and C−H Alkenylation of Indoles with 1,3‐Diynes by C−H Activation

et al. 2021

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Described herein is the Rh(III)-catalyzed [3 + 2] annulations and C2-alkenylations of indoles with 1,3-diynes, which deliver the synthetically important 3H-pyrrolo[1,2-a]indol-3-ones and highly functionalized tetrasubstituted olefin derivatives. Importantly, in this methodology, the additive controlled selective formation of desired scaffolds. This synthetic strategy exhibits high efficiency and broad functional group compatibility. Furthermore, this protocol has been successfully extended to the synthesis of bisannulated and trisubstituted alkenes. The method is also smoothly applied for the synthesis of the core structure of protein kinase C inhibitor and melatonin analogues.

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Section: Methodsmentioning

confidence: 99%

Rh(III)‐Catalyzed [3+2] Annulation and C−H Alkenylation of Indoles with 1,3‐Diynes by C−H Activation

et al. 2021

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“…The work by Fei Zhao, Xiaowei Wu, and Xiaoning Zhang, and co-workers in 2021 introduced a rhodium-catalyzed redox neutral additive controlled switchable synthesis of tetrasubstituted 1,3-enynes 67 and alkynylated 3H-pyrrolo[1,2-a] indol-3-ones 65 (Scheme 45). 26 High regio-and stereo-selectivity, as well as selective mono-functionalization over di-functionalization, are the notable features of this reaction.…”

Section: Scheme 44 Control Experimentsmentioning

confidence: 99%

Transition Metal-catalyzed C-H /C-C Activation and Coupling with 1, 3-diyne

Pati

Puthalath

Banjare

et al. 2022

Preprint

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This review focuses on providing a broad overview of the recent developments in the field of transition metal-catalyzed C-H bond activation and coupling with 1,3-diyne for assembling alkynylated heterocycles and bis-heterocycles. In recent years the use of 2π-unsaturated units as coupling partners for the synthesis of heterocycles through C-H bond activation and an-nulation sequence has received immense attention. Among the unsaturated units employed for assembling heterocycles, the use of 1,3-diynes has garnered significant attention due to its ability in rendering the straightforward bis-heterocycles. Earlier methods employed to assemble bis-heterocycle include the use of preformed and pre-functionalized heterocycles via transi-tion metal-catalyzed coupling reactions. The expensive pre-functionalized halo-heterocycles and sensitive & expensive heterocyclic metal reagents limit its use. However, the transition metal-catalyzed C-H activation obviates the need for expensive heterocyclic metal reagents and pre-functionalized halo-heterocycles. The C-H bond activation strategy makes use of C-H bonds as functional groups for effecting the transformation. This renders the overall synthetic sequence both step and costs economic. Hence, this strategy of C-H activation and subsequent reaction with 1,3-diyne is useful for the larger-scale synthesis of chemicals in the pharmaceutical industry. Despite these advances, there is still the possibility of exploration of earth-abundant, and cost-effective first-row transition metals (Ni, Cu, Mn. Fe, etc.) for the synthesis of bis-heterocycles. Moreover, the Cp* ligand free, simple metal salt mediated synthesis of bis-heterocycles is also less explored. Thus, more exploration of reaction conditions for the Cp* free synthesis of bis-heterocycles is called for. We hope this review will inspire scientists to explore the unexplored domains.

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“…Moreover, despite the remarkable advantages such as excellent stereoselectivity and high atom‐economy, this method still shows some minor drawbacks such as the usage of excessive additives and the requirement of chromatography for the purification of products. Considering the low cost and outstanding catalytic performance of Ru catalysts in C−H activation, [14] and together with our interests in TM‐catalyzed C−H functionalization [11d–g,12,15] and indole compound synthesis, [16] herein we report an efficient Ru(II)‐catalyzed C−H alkenylation/DG migration cascade between N ‐carbamoyl indoles and alkynes for the regio‐ and stereoselective assembly of tetrasubstituted alkenes carrying the privileged indole substituent (Scheme 2c). Notably, the carbamoyl DG [17] is endowed with a dual role of auxiliary group and internal acylation reagent via C−N bond cleavage, which migrates onto the alkene moiety of the products to deliver tetrasubstituted α,β‐unsaturated amides.…”

Section: Introductionmentioning

confidence: 99%

Regio‐ and Stereoselective Synthesis of Tetrasubstituted Alkenes via Ruthenium(II)‐Catalyzed C–H Alkenylation/Directing Group Migration

Mao

Zhao

2022

ChemistrySelect

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Herein we report the regio-and stereoselective synthesis of tetrasubstituted alkenes from N-carbamoyl indoles and alkynes via ruthenium(II)-catalyzed CÀ H alkenylation/directing group migration, in which the carbamoyl directing group is endowed with a dual role of auxiliary group and migrating acylation reagent via CÀ N bond cleavage. This method features broad substrate scope, high atom-and step-economy, good functional group tolerance and mild redox-neutral conditions at room temperature. A series of structurally diverse tetrasubstituted alkenes were synthesized in good to excellent yields, highlighting the efficiency of this method.

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Additive-Controlled Divergent Synthesis of Tetrasubstituted 1,3-Enynes and Alkynylated 3H-Pyrrolo[1,2-a]indol-3-ones via Rhodium Catalysis

Cited by 49 publications

References 134 publications

Rh(III)‐Catalyzed [3+2] Annulation and C−H Alkenylation of Indoles with 1,3‐Diynes by C−H Activation

Rh(III)‐Catalyzed [3+2] Annulation and C−H Alkenylation of Indoles with 1,3‐Diynes by C−H Activation

Transition Metal-catalyzed C-H /C-C Activation and Coupling with 1, 3-diyne

Regio‐ and Stereoselective Synthesis of Tetrasubstituted Alkenes via Ruthenium(II)‐Catalyzed C–H Alkenylation/Directing Group Migration

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