A mild and efficient Pd-catalyzed cyclopropanation of norbornene derivatives with tertiary propargylic alcohols using molecular oxygen as the sole oxidant is described. This process allows quick and atom-economical assembly of various 1,2,3-trisubstituted cyclopropanes bearing α,β-unsaturated ketone moieties in high yields as a single regio- and diastereoisomer.
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http://dx.doi.org/10.1039/c2cc35124b | DOI Listing |
Biosensors (Basel)
December 2022
Research Center for Molecular Mechanisms of Aging and Age-Related Diseases, Moscow Institute of Physics and Technology, 141701 Dolgoprudny, Russia.
Dicyclopropanated 5-vinyl-2-norbornene (dcpVNB) is a strained polycyclic hydrocarbon compound with a high energy content, which makes it promising for the development of propellant components based on it. In this work, the genotoxic properties of dcpVNB were studied using whole-cell -biosensors based on and . It was shown that the addition of dcpVNB to bacterial cells leads to the appearance of DNA damage inducing the SOS response and Dps expression with slight activation of the OxyR-mediated response to oxidative stress.
View Article and Find Full Text PDFNat Chem
December 2019
Department of Chemistry, University of Chicago, Chicago, IL, USA.
All-carbon tetrasubstituted olefins have been found in numerous biologically important compounds and organic materials. However, regio- and stereocontrolled construction of this structural motif still constitutes a significant synthetic challenge. Here, we show that a modular and regioselective synthesis of all-carbon tetrasubstituted olefins can be realized via alkenyl halide- or triflate-mediated palladium/norbornene catalysis, which is enabled by a modified norbornene containing a C2 amide moiety.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2017
Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
An enantioselective C-H addition to a C=C bond represents the most atom-efficient route for the construction of chiral carbon-carbon skeletons, a central research topic in organic synthesis. We herein report the enantioselective yttrium-catalyzed C(sp )-H bond addition of 2-methyl azaarenes, such as 2-methyl pyridines, to various substituted cyclopropenes and norbornenes. This process efficiently afforded a new family of chiral pyridylmethyl-functionalized cyclopropane and norbornane derivatives in high yields and high enantioselectivities (up to 97 % ee).
View Article and Find Full Text PDFJ Org Chem
October 2014
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
This Note details experiments that probe the mechanism by which donor-acceptor norbornene systems epimerize. A number of mechanistic studies indicate that epimerization in these systems occurs via a Lewis acid catalyzed retro-Diels-Alder/Diels-Alder sequence, rather than bond rotation in an intimate ion pair. These results suggest that, under the reaction conditions examined, the ring strain present in norbornene is inadequate to induce zwitterion formation analogous to that observed with donor-acceptor cyclopropanes.
View Article and Find Full Text PDFJ Org Chem
June 2014
Department of Chemistry, Graduate School of Science and ‡Research Institute of Green Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan.
Propargyl acetates reacted with norbornene in the presence of a catalytic amount of tetrakis(tripheylphosphine)palladium to give cyclopropyl ketones. The reaction proceeded with high stereoselectivity, affording a single stereoisomer. The reaction of various substituted norbornenes gave the corresponding cyclopropanes in moderate to good yields.
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