A silver-catalyzed vinylogous fluorination of vinyl diazoacetates to generate γ-fluoro-α,β-unsaturated carbonyls is presented. Application of this method to the fluorination of farnesol and steroid derivatives was achieved.
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http://dx.doi.org/10.1021/ol403017e | DOI Listing |
Chemistry
April 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India) .
An asymmetric double desymmetrization methodology has been developed for synthesizing densely functionalized chiral cyclopentylcyclohexane scaffolds. We have constructed four chiral centers, including an all-carbon quaternary stereocenter in a single C-C bond formation event. The methodology has high functional-group tolerance and delivers a broad range of enantioenriched products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2023
Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona (UdG), Facultat de Ciències, C/ Maria Aurèlia Capmany, 69, 17003 Catalunya, Girona, Spain.
The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp )-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process. A Tp -containing silver complex first promotes the generation of a donor-acceptor silver carbene which triggers CAM, generating a subsequent donor-donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp )-H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C-H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step.
View Article and Find Full Text PDFChem Commun (Camb)
December 2020
Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi-110016, India.
A silver tetrafluoroborate catalyzed domino cycloisomerization-vinylogous aldol addition sequence on a multifunctional substrate such as ortho-alkynylbenzaldehydes yielding functionalized 1H-isochromenes in a single step with high yield and excellent diastereoselectivity (>19 : 1) is described. The reaction was well tolerated by alkyl, aryl, and unsubstituted alkynylbenzaldehydes, and furnished selective 6-endo-dig adducts exclusively without loss in the regio- as well as diastereoselectivity.
View Article and Find Full Text PDFOrg Biomol Chem
July 2018
Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1, Inohana, Chuo-ku, Chiba 260-8675, Japan. and Molecular Chirality Research Center, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
A simple protocol to directly access γ-amino acid derivatives by intermolecular regioselective hydroamination of trichloroethyl alkenyldiazoacetates with carbamate using a silver tetrafluoroborate catalyst is described. Density functional theory (DFT) calculations to analyze the reaction mechanism revealed that multiple attractive interactions occur in a transition state to promote the vinylogous addition of nitrogen nucleophiles.
View Article and Find Full Text PDFOrg Lett
December 2013
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, United States.
A silver-catalyzed vinylogous fluorination of vinyl diazoacetates to generate γ-fluoro-α,β-unsaturated carbonyls is presented. Application of this method to the fluorination of farnesol and steroid derivatives was achieved.
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