Visible light promoted deaminative difluoroalkylation of aliphatic amines with difluoroenoxysilanes

Huang, Yang; Jia, Jia; Huang, Qi-Ping; Zhao, Liang; Wang, Pan; Gu, Jiwei; He, Chun‐Yang

doi:10.1039/d0cc05725h

Cited by 25 publications

(8 citation statements)

References 45 publications

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“…In addition, product 3 a could either be readily reduced to homoallylic alcohol 6 in the presence of NaBH 4 or be converted into propargylic alcohol 7 after reacting with TMS‐substituted acetylene followed by cleavage of the TMS group under basic conditions. Moreover, by treating the carbonyl group in product 3 a with DAST, bisfluorination occurred to give tetrafluoroethylene chain (−CF 2 CF 2 −) in product 8 , which has potential applications in the fields of materials and agrochemicals [4o] …”

Section: Resultsmentioning

confidence: 99%

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

et al. 2022

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The reaction of non‐fluorinated silyl enol ether with alkyne is useful for the synthesis of β,γ‐unsaturated carbonyl compounds. However, most of the existing methods for realizing such organic transformation usually employ stoichiometric amounts of relatively expensive Lewis acids/metallic salts. Herein, an iron(III)‐catalyzed difluoroalkylation of aryl alkynes with difluoroenol silyl ether was developed. The reactions proceeded smoothly in the presence of a catalytic amount of iron(III) chloride, stoichiometric amounts of trimethylsilyl chloride, and 4 Å molecular sieves in dichloroethane (DCE) to afford the corresponding α‐alkenyl‐α,α‐difluoroketones in modest to good yields. Remarkably, among the various metallic salts screened, cheap and less‐toxic iron(III) salt was found to be the most efficient Lewis acid catalyst for the present reaction. In addition, in the absence of iron(III) chloride or trimethylsilyl chloride, either no reaction occurred or considerably reduced reaction performance was observed. Moreover, the use of Brønsted acid to replace iron(III) chloride as reaction catalyst failed to promote the reaction. The reaction could be scaled up and the obtained difluoroalkylated carbonyl compound serves as a versatile building block which could be subjected to late‐stage diversification to be converted into useful organic molecules containing CF2H and CF2CF2 moieties. Deuterated experiments showed that the proton in the generated alkene product should originate from trace amounts of water present in the reaction system.

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Section: Resultsmentioning

confidence: 99%

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

et al. 2022

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“…In this protocol, commercially available 2‐bromo‐3,3,3‐trifluoropropene (BTP) [33–35] serves as a radical acceptor for the first time (Scheme 2b) [36] . In addition to carboxylic acids, amines can also be used as radical precursors through a deaminative process when transformed to Katritzky salts [37–46] . Amines are widely found in diverse organic compounds, and are commercially available.…”

Section: Introductionmentioning

confidence: 99%

“…[36] In addition to carboxylic acids, amines can also be used as radical precursors through a deaminative process when transformed to Katritzky salts. [37][38][39][40][41][42][43][44][45][46] Amines are widely found in diverse organic compounds, and are commercially available. Herein, we report a general deaminative crosscoupling of Katritzky salts with 2-bromo-3,3,3-trifluoropropene (BTP) that is facilitated by an electron-donor-acceptor (EDA) complex to afford α-trifluoromethylated alkyl bromides.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Secondary Trifluoromethylated Alkyl Bromides with Further Conversion to Boronic Esters and Alcohols

Li,

Mao,

Yang

et al. 2023

Asian J Org Chem

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Secondary trifluoromethylated alkyl bromides are versatile building blocks in the synthesis of fluorine‐containing aliphatic compounds. However, current methods of preparation are limited. In this study, we have developed a general deaminative cross‐coupling of Katritzky salts with 2‐bromo‐3,3,3‐trifluoropropene (BTP) as a route to α‐trifluoromethylated alkyl bromides that is driven by an electron‐donor‐acceptor (EDA) complex. The resultant products can be readily converted to α‐trifluoromethyl borates and α‐trifluoromethyl alcohols, enriching the current toolbox for synthesizing trifluoromethylated aliphatic compounds with wide‐ranging applications.

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“…Difluoroenoxysilanes 1 have recently been identified as a family of versatile synthetic building blocks for accessing functionalized gem -difluoroketones . In this regard, a variety of catalytic C–C bond-forming reactions involving 1 has been developed, such as aldol, conjugate addition, cross-coupling, Mannich, olefination, propargylation, and others, allowing the diverse construction of value-added α,α-difluoroketones . Despite great advances based on these C -site reactions of difluoroenoxysilanes 1 (left, Scheme B), the O -site reactivity of 1 has never been explored.…”

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confidence: 99%

Construction of gem-Difluoroenol Esters through Catalytic O-Selective Addition of Difluoroenoxysilanes to Ketenes

Shi

Pan

et al. 2021

J. Org. Chem.

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The O-site reactivity of difluoroenoxysilanes is disclosed for the first time, which enabled the direct construction of versatile gem-difluoroalkenes through an unprecedented highly efficient addition reaction with ketenes. A series of valuable gem-difluoroenol esters were achieved in good to excellent yields. The synthetic versatility of this protocol is further demonstrated by the gram-scale synthesis and good functional group tolerance.

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Visible light promoted deaminative difluoroalkylation of aliphatic amines with difluoroenoxysilanes

Abstract: A visible light promoted deaminative strategy for the difluoroalkylation reaction utilizing pyridinium activated aliphatic primary amines and difluoroenoxysilane as substrates have been developed. This protocol is characteriazed by its mild...

Cited by 25 publications

References 45 publications

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

Synthesis of Secondary Trifluoromethylated Alkyl Bromides with Further Conversion to Boronic Esters and Alcohols

Construction of gem-Difluoroenol Esters through Catalytic O-Selective Addition of Difluoroenoxysilanes to Ketenes

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