Chemical Science, Год журнала: 2024, Номер 15(34), С. 13800 - 13806
Опубликована: Янв. 1, 2024
Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved double-bond metathesis, like olefin metathesis and carbonyl single-bond has received less attention the past decade. Herein, we describe first C(sp
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)
Опубликована: Март 22, 2024
Abstract The use of gem ‐difluorinated cyclopropanes ( ‐DFCPs) as fluoroallyl surrogates under transition‐metal catalysis has drawn considerable attention recently but such reactions are restricted to producing achiral or racemic mono‐fluoroalkenes. Herein, we report the first enantioselective allylation indoles rhodium with ‐DFCPs. This reaction shows exceptional branched regioselectivity towards ‐DFCPs, which provides an efficient route enantioenriched fluoroallylated wide substrate scope and good functional group tolerance.
Язык: Английский
Процитировано
15
Chemical Communications, Год журнала: 2024, Номер 60(28), С. 3764 - 3773
Опубликована: Янв. 1, 2024
This feature article summarizes our efforts towards developing Rh-catalyzed reactions of gem -difluorinated cyclopropanes, briefly discussing the design, selectivity, mechanisms and future research prospects.
Язык: Английский
Процитировано
12
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)
Опубликована: Фев. 27, 2024
A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino bearing a linear 2-fluoroallylic motif, which served as an appealing platform for construction other valuable enantioenriched compounds. The key intermediates were confirmed HRMS detection, while DFT calculations revealed that excellent enantioselectivity was attributed to stabilizing non-covalent interactions Pd(II)-π-fluoroallyl species Ni(II)-Schiff base complex.
Язык: Английский
Процитировано
11
ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4287 - 4293
Опубликована: Фев. 25, 2025
Язык: Английский
Процитировано
1
Chemical Science, Год журнала: 2021, Номер 12(47), С. 15511 - 15518
Опубликована: Янв. 1, 2021
Modulating the reaction selectivity is highly attractive and pivotal to rational design of synthetic regimes. The defluorinative functionalization
Язык: Английский
Процитировано
45
Synlett, Год журнала: 2022, Номер 34(01), С. 1 - 13
Опубликована: Июль 28, 2022
Abstract As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties as result the gem-difluoro substitution; thus, their reactions received much attention from synthetic chemistry community. Recently, gradually emerged type novel and unique fluorinated allylic synthon in cross-coupling for synthesis monofluoroalkenes. Herein, we briefly summarize recent advances transition-metal-catalyzed cyclopropanes. 1 Introduction 2 Palladium-Catalyzed Reactions with Linear Selectivity 3 Branched 4 Other Metal-Catalyzed 5 Conclusions
Язык: Английский
Процитировано
38
Chinese Journal of Chemistry, Год журнала: 2022, Номер 40(19), С. 2345 - 2355
Опубликована: Июнь 28, 2022
Comprehensive Summary Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules. Here, we report a method for the selective construction of these compounds diversity‐oriented fashion through regiodivergent cross‐coupling gem ‐difluorocyclopropanes with allylboronates by employing palladium catalyst two different ligands, which were used as allyl electrophiles C—C C—F bond activation. In presence 2‐biphenylyl(diphenyl)phosphine ligand, linear‐selective allyl–allyl formation is highly obtained, while utilizing sterically hindered BrettPhos (dicyclohexyl[3,6‐dimethoxy‐2',4',6'‐tris(1‐methylethyl)[1,1'‐biphenyl]‐2‐yl]phosphine) ligand favors generation branched‐selective product. Experimental computational studies investigated key steps reactions, revealing origin ligand‐controlled regiodivergence.
Язык: Английский
Процитировано
36
Organic Letters, Год журнала: 2022, Номер 24(28), С. 5051 - 5055
Опубликована: Июль 14, 2022
A new Co-catalyzed sequential C-C and C-F activation of gem-difluorinated cyclopropanes (gem-FCPs) to form nucleophilic fluoroallylcobalt, followed by addition aldehydes, is reported. The protocol features the regioselective cleavage dual chemical bonds readily available gem-FCPs prepare easily separable linear (Z)- (E)-fluorinated homoallylic alcohols with a broad scope. This discovery established strategy for efficient transformation as well synthesis challenging fluorinated alcohols.
Язык: Английский
Процитировано
36
Chemical Science, Год журнала: 2022, Номер 13(42), С. 12419 - 12425
Опубликована: Янв. 1, 2022
The control of linear/branched selectivity is one the major focuses in transition-metal catalyzed allyl-allyl cross-coupling reactions, which bond connection occurs at terminal site both allyl fragments forming different types 1,5-dienes. Herein, terminal/internal regioselectivity investigated and found to be switchable reactions between gem-difluorinated cyclopropanes allylboronates. controlled arises from fine-tuning rhodium catalytic system. Fluorinated 1,3-dienes, 1,4-dienes 1,5-dienes are therefore produced good yields with respectively isomerized terminal, internal, regioselectivity.
Язык: Английский
Процитировано
32
The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3787 - 3793
Опубликована: Фев. 24, 2023
Fluorinated compounds have found widespread applications in pharmaceuticals, agrochemicals, and materials science. Precise construction of α-difluoromethylene ether (CF2-O) moiety organic molecules is high demand. Herein, a visible light-promoted reaction protocol for the synthesis from gem-difluorocyclopropane described. The key ring-opening step induced by hyperconjugative interaction cyclopropane with photo-oxidized aromatic rings. This easy scale-up, products bearing synthetic handle enable their further manipulation.
Язык: Английский
Процитировано
17