334-68-9Relevant articles and documents
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Pattison,Norman
, p. 2311,2315 (1957)
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Landini,D. et al.
, p. 428 - 430 (1974)
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Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor
González-Esguevillas, María,Miró, Javier,Jeffrey, Jenna L.,MacMillan, David W.C.
supporting information, p. 4222 - 4227 (2019/06/13)
Herein we disclose a deoxyfluorination of alcohols with an electrophilic fluorine source via visible-light photoredox catalysis. This radical-mediated C–F coupling is capable of fluorinating secondary and tertiary alcohols efficiently, complementing previously reported nucleophilic deoxyfluorination protocols.
Mechanism of Copper-Catalyzed Hydroalkylation of Alkynes: An Unexpected Role of Dinuclear Copper Complexes
Suess, Alison M.,Uehling, Mycah R.,Kaminsky, Werner,Lalic, Gojko
supporting information, p. 7747 - 7753 (2015/06/30)
This article describes a mechanistic study of copper-catalyzed hydroalkylation of terminal alkynes. Relying on the established chemistry of N-heterocyclic carbene copper hydride (NHCCuH) complexes, we previously proposed that the hydroalkylation reaction proceeds by hydrocupration of an alkyne by NHCCuH followed by alkylation of the resulting alkenylcopper intermediate by an alkyl triflate. NHCCuH is regenerated from NHCCuOTf through substitution with CsF followed by transmetalation with silane. According to this proposal, NHCCuH must react with an alkyne faster than with an alkyl triflate to avoid reduction of the alkyl triflate. However, we have determined that NHCCuH reacts with alkyl triflates significantly faster than with terminal alkynes, strongly suggesting that the previously proposed mechanism is incorrect. Additionally, we have found that NHCCuOTf rapidly traps NHCCuX (X = F, H, alkenyl) complexes to produce (NHCCu)2(μ-X)(OTf) (X = F, H, alkenyl) complexes. In this article, we propose a new mechanism for hydroalkylation of alkynes that features dinuclear (NHCCu)2(μ-H)(OTf) (X = F, H, alkenyl) complexes as key catalytic intermediates. The results of our study establish feasible pathways for the formation of these intermediates, their ability to participate in the elementary steps of the proposed catalytic cycle, and their ability to serve as competent catalysts in the hydroalkylation reaction. We also provide evidence that the unusual reactivity of the dinuclear complexes is responsible for efficient hydroalkylation of alkynes without concomitant side reactions of the highly reactive alkyl triflates. (Figure Presented).
