Deaminative bromination, chlorination, and iodination of primary amines

Xue, Jiang-Hao; Li, Yin; Tan, Dong‐Hang; Tu, Fang-Hai; Liu, Yuan; Li, Qingjiang; Wang, Honggen

doi:10.1016/j.isci.2023.106255

Cited by 4 publications

(3 citation statements)

References 74 publications

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“…Based on the aforementioned results and preceding reports, 56,[58][59][60] a mechanistic scenario has been proposed to rationalize the observed reaction outcomes, as illustrated in Scheme 4.…”

Section: Scheme 4 Plausible Mechanismmentioning

confidence: 84%

“…[53][54] We are fascinated by the recent renaissance of 1,1-diazene chemistry, which has proven successful in various challenging transformations, such as deaminative ring contraction, [55][56][57] reduction, 58 and functionalization reactions. [59][60] Mechanistically, the formation of the 1,1-diazene intermediate is achieved through the reaction of an amine with either an N-anomeric amide 56,58 or an in-situ-generated iodonitrene, 57 or via a Curtius-type rearrangement of sulfamoyl azide. 55,61 Subsequently, this intermediate can undergoe thermal homolytic N2 extrusion to form a geminate radical pair, which can undergo either in-cage radical recombination or out-cage radical trapping to form the final products.…”

Section: Introductionmentioning

confidence: 99%

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Site-specific Deaminative Trifluoromethylation of Aliphatic Primary Amines

Wang,

Xue,

et al. 2023

Preprint

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The introduction of trifluoromethyl groups into organic molecules is of paramount importance in modern synthetic chemistry and medicinal chemistry. While methods for constructing C(sp2)-CF3 bonds have been well established, the advancement of practical and comprehensive approaches for forming C(sp3)-CF3 bonds remains considerably restricted. In this work, we describe an efficient and site-specific deaminative trifluoromethylation reaction of aliphatic primary amines to afford the corresponding alkyl trifluoromethyl compounds. The reaction proceeds at room temperature with readily accessible N-anomeric amide and bench-stable bpyCu(CF3)3 (Grushin’s reagent) under blue light. The protocol features mild reaction conditions, good functional group tolerance, and moderate to good yields. Remarkably, the method can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules. Experimental mechanistic studies were conducted, and a radical mechanism is proposed, wherein the dual roles of Grushin’s reagent have been elucidated.

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Section: Scheme 4 Plausible Mechanismmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Site-specific Deaminative Trifluoromethylation of Aliphatic Primary Amines

Wang,

Xue,

et al. 2023

Preprint

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“…17 The transformation relies on the facile in situ generation of an isodiazene intermediate, which can undergo thermal homolytic N 2 extrusion to forms a new C–C bond. 17 a Inspired by N -anomeric amide's excellent electrophilic properties 17,18 and our long-term interest in organosulfur chemistry, 19 we initially programmed a project aiming at the formation of S–S bonds starting from thiols. Subsequently, we have successfully detected of disulfide product when the reaction was conducted in thiol with Levin's reagent at room temperature (Scheme 1(b)).…”

Section: Introductionmentioning

confidence: 99%

Facile and efficient transformation of thiols to disulfides via a radical pathway with N-anomeric amide

Xu,

Yan,

Huang

et al. 2024

RSC Adv.

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Site‐Specific Deaminative Trifluoromethylation of Aliphatic Primary Amines**

Xue,

Li,

Liu

et al. 2024

Angewandte Chemie

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The introduction of trifluoromethyl groups into organic molecules is of paramount importance in modern synthetic chemistry and medicinal chemistry. While methods for constructing C(sp2)‐CF3 bonds have been well established, the advancement of practical and comprehensive approaches for forming C(sp3)‐CF3 bonds remains considerably restricted. In this work, we describe an efficient and site‐specific deaminative trifluoromethylation reaction of aliphatic primary amines to afford the corresponding alkyl trifluoromethyl compounds. The reaction proceeds at room temperature with readily accessible N‐anomeric amide (Levin’s reagent) and bench‐stable bpyCu(CF3)3 (Grushin’s reagent) under blue light. The protocol features mild reaction conditions, good functional group tolerance, and moderate to good yields. Remarkably, the method can be applied to the direct, late‐stage trifluoromethylation of natural products and bioactive molecules. Experimental mechanistic studies were conducted, and a radical mechanism is proposed, wherein the dual roles of Grushin’s reagent have been elucidated.

show abstract

Deaminative bromination, chlorination, and iodination of primary amines

Cited by 4 publications

References 74 publications

Site-specific Deaminative Trifluoromethylation of Aliphatic Primary Amines

Site-specific Deaminative Trifluoromethylation of Aliphatic Primary Amines

Facile and efficient transformation of thiols to disulfides via a radical pathway with N-anomeric amide

Site‐Specific Deaminative Trifluoromethylation of Aliphatic Primary Amines**

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