An efficient Ru-catalyzed regioselective allylic trifluoromethylthiolation reaction of allylic carbonates was developed. The linear allylic trifluoromethyl thioethers were obtained in 52-91% yields. Mechanistic investigation revealed that this reaction proceeds via a double allylic trifluoromethylthiolation sequence.
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http://dx.doi.org/10.1021/jo5019393 | DOI Listing |
Acc Chem Res
September 2022
Institute of Organic Chemistry & MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510006, P. R. China.
Asymmetric electrophilic reactions provide an ideal method for the construction of chiral molecules by incorporating one or more functional groups into the parent substrates under mild conditions. However, due to the issues of the reactivities of electrophilic species and the possible racemization of chiral intermediates as well as the restriction of the chiral scaffolds of chiral catalysts, many limitations remain in this field, such as the narrow scopes of substrates and electrophiles as well as the limited types of nucleophiles and reactions. To overcome the limitations in the synthesis of diversified chiral molecules, we developed a series of indane-based chiral amino aryl chalcogenide catalysts.
View Article and Find Full Text PDFJ Org Chem
August 2022
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
A metal-free visible-light-induced trifluoromethylation of Bunte salts of α-bromoketones/alkyl bromide/benzyl bromides/functionalized allyl (Baylis-Hillman) bromides has been accomplished using Langlois' reagent in the presence of inexpensive eosin Y as a photocatalyst to form the privileged trifluoromethylthiolated synthons. The method is straightforward, operationally simple, and endowed with broad substrate scope and good functional group tolerance.
View Article and Find Full Text PDFAcc Chem Res
April 2022
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster, Germany.
The carbonyl group stands as a fundamental scaffold and plays a ubiquitous role in synthetically important chemical reactions in both academic and industrial contexts. Venerable transformations, including the aldol reaction, Grignard reaction, Wittig reaction, and Nozaki-Hiyama-Kishi reaction, constitute a vast and empowering synthetic arsenal. Notwithstanding, two-electron mechanisms inherently confine the breadth of accessible reactivity and topological patterns.
View Article and Find Full Text PDFOrg Lett
October 2020
School of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs and Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, P.R. China.
A selenium-catalyzed trifluoromethylthiolation/[2,3]-sigmatropic rearrangement of tertiary allylic and propargylic alcohols which could provide straightforward and facile access to trifluoromethyl sulfoxides was developed. Various allylic and allenic trifluoromethyl sulfoxides were obtained with moderate to excellent yields. Meanwhile, a Lewis acid mediated trifluoromethylthiolation/1,2-rearrangement to synthesize β-SCF carbonyl compounds was also accomplished.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2020
Institute of Organic Chemistry & MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
An unprecedented approach for efficient synthesis of functionalized allylic gem-difluorides via catalytic fluorinative Meyer-Schuster-like rearrangement is disclosed. This transformation proceeded with readily accessible propargylic fluorides, and low-cost B-F reagents and electrophilic reagents by sulfide catalysis. A series of iodinated, brominated, and trifluoromethylthiolated allylic gem-difluorides that were difficult to access by other methods were facilely produced with a wide range of functional groups.
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