Organic Letters, Journal Year: 2021, Volume and Issue: 23(15), P. 6153 - 6157
Published: July 16, 2021
An efficient visible-light-promoted N-radical-mediated tandem radical cyclization/defluorinated alkylation of β,γ-unsaturated hydrazones, and α-trifluoromethyl alkenes is described. This protocol provides a general effective route to synthesize various dihydropyrazole-fused gem-difluoroalkenes at moderate excellent yields under redox-neutral, metal-free, mild conditions.
Language: Английский
Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(14), P. 3915 - 3942
Published: Jan. 1, 2021
The C–F bond is the strongest single in organic compounds.
Language: Английский
Citations
156
Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(2), P. 234 - 267
Published: Nov. 29, 2021
Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image
Language: Английский
Citations
124
Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11602 - 11610
Published: July 22, 2021
Herein we report a chromium-catalyzed allylic defluorinative ketyl olefin coupling between aldehydes and α-trifluoromethyl alkenes, which provides novel efficient access to diverse gem-difluorohomoallylic alcohols. Remarkably, the high chemoselectivity of this reaction enables conversion formyl moiety in presence various easily reducible functionalities including ketone, organohalides, aziridine, sulfone, alkyne, unactivated alkene. The utility method is demonstrated by simple derivatizations attached hydroxyl group products. preliminary mechanistic investigations suggest pathway with rate-limiting C–C forming step followed facile β-fluoro elimination.
Language: Английский
Citations
115
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)
Published: Aug. 22, 2023
Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.
Language: Английский
Citations
60
Organic Letters, Journal Year: 2021, Volume and Issue: 23(6), P. 2353 - 2358
Published: March 10, 2021
Herein, we report a method that combines hydrogen atom transfer and photoredox catalysis to achieve the dehydrogenative difluoroallylation of amides, ethers, alkyl aldehydes. This operationally convenient transforms broad scope substrates into corresponding gem-difluoroalkenes via construction C(sp3)–C(sp3) or C(sp3)–C(sp2) bonds. Excellent functional group compatibility high selectivity make this have wide range substrate types render it suitable for late-stage modification pharmaceutical intermediates.
Language: Английский
Citations
81
Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(10), P. 2315 - 2327
Published: Jan. 1, 2021
The
latest
achievements
in
the
catalytic
asymmetric
synthesis
of
both
monofluoro-
and
Language: Английский
Citations
79
Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)
Published: Oct. 7, 2020
Abstract Alkyl carboxylic acids as well primary amines are ubiquitous in all facets of biological science, pharmaceutical chemical science and materials science. By conversion to redox-active esters (RAE) Katritzky’s N -alkylpyridinium salts, respectively, alkyl serve ideal starting forge new connections. In this work, a Mn-mediated reductive decarboxylative/deaminative functionalization activated aliphatic is disclosed. A series C-X (X = S, Se, Te, H, P) C-C bonds efficiently constructed under simple mild reaction conditions. The protocol applicable the late-stage modification some structurally complex natural products or drugs. Preliminary mechanistic studies suggest involvement radicals pathway.
Language: Английский
Citations
77
Chemical Communications, Journal Year: 2021, Volume and Issue: 58(8), P. 1066 - 1077
Published: Dec. 24, 2021
Fluorine-containing molecules have found broad applications in pharmaceutical and agrochemical industries as introducing fluorine into a molecule could significantly tune the biological activities of parent molecules. Thus, synthesis fluorine-containing has received substantial attention over past few decades. As complementary strategy for fluorinated compounds through new Csp3-F bonds formation, selective cleavage inert from easily-available cost-effective multifluorinated molecules, such fluoroalkylaromatics, α-trifluoromethyl alkenes α-multifluorinated carbonyl compounds, been emerging an attractive alternative to access Moreover, inherent nature radical reactions offers opportunity functionalizations occur under mild conditions. In this regard, development photoredox catalysis, transition-metal or electrochemistry enable species generation via gained progress made recent years. This highlight summerizes advances single-electron-transfer enabled pathways.
Language: Английский
Citations
65
ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(19), P. 11960 - 11965
Published: Sept. 13, 2021
A cross-electrophile coupling between gem-difluorinated cyclopropanes and 2,2-difluorovinyl tosylate via dual Ni/Pd cooperative catalysis under mild reaction conditions is presented. Various structurally unique organofluorine compounds bearing both monofluoroalkene gem-difluoroalkene moieties can be effectively afforded in good yields with a high (Z)-selectivity. The synthetic utility of this protocol has been successfully demonstrated by the late-stage modification series complex bioactive molecules.
Language: Английский
Citations
61
Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(7), P. 2013 - 2055
Published: Jan. 1, 2022
We highlighted the recent advances in field of multiple-fold C–F bond functionalization for synthesis (hetero)cyclic compounds.
Language: Английский
Citations
48