Organic Letters, Journal Year: 2024, Volume and Issue: 26(48), P. 10317 - 10321
Published: Nov. 21, 2024
Synthesis of
Language: Английский
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 24 - 32
Published: Oct. 13, 2023
Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, efficient Pd/IPr
Language: Английский
Citations
35
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)
Published: Aug. 12, 2023
Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated
Language: Английский
Citations
31
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)
Published: March 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.
Language: Английский
Citations
18
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)
Published: Jan. 10, 2024
Here we present a modular, chemo-, regio-, and stereoselective synthesis of fully-substituted configuration-defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo- regioselective functionalization CF
Language: Английский
Citations
13
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)
Published: Feb. 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.
Language: Английский
Citations
13
Chemical Communications, Journal Year: 2024, Volume and Issue: 60(28), P. 3764 - 3773
Published: Jan. 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.
Language: Английский
Citations
13
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)
Published: April 2, 2024
The diversified synthesis of chiral fluorinated cyclobutane derivatives has remained a difficult task in synthetic chemistry. Herein, we present an approach for asymmetric hydroboration and formal hydrodefluorination gem-difluorinated cyclobutenes through rhodium catalysis, providing α-boryl cyclobutanes monofluorinated with excellent regio- enantioselectivity, respectively. key to the success two transformations relies on efficient, mild highly selective rhodium-catalyzed HBPin (pinacolborane), which subsequent addition base, catalytic amount palladium some cases, results formation products four-membered ring retained. obtained are versatile building blocks that provide platform enantioenriched great diversity.
Language: Английский
Citations
12
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: May 21, 2024
Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by inherent preference an inner-sphere mechanism. Here, we present a demonstration outer-sphere mechanism in Rh-catalyzed reaction simple using gem -difluorinated cyclopropanes as allyl surrogates. This unconventional offers opportunity fluorine recycling via C − F bond cleavage/reformation, ultimately delivering carbofluorination products. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and -difluorides with 100% atom economy. DFT calculations reveal that formation goes through unusual nucleophilic allyl-Rh species instead migration insertion, generated carbon cation then forms tetrafluoroborate fluoride shuttle.
Language: Английский
Citations
12
Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 20, 2025
Language: Английский
Citations
2
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 17, 2025
gem-Difluorinated carbocyclic rings are attractive motifs in drug development. Herein, we report the transition-metal free cascade reaction of bicyclo[1.1.0]butanes (BCBs) with gem-difluorocyclopropenes for synthesis gem-difluorinated excellent regio- and diastereoselectivity. This method was successfully applied to provide a broad range cyclopentenes cyclopropanes, which could undergo variety difluoromethylene (CF2) retaining transformations.
Language: Английский
Citations
1