Publication

Enantioselective Ruthenium(II)-Catalyzed Access to Benzonorcaradienes by Coupling of Oxabenzonorbornadienes and Alkynes

Abstract

Benzonorcaradienes and benzonorcarenes are attractive scaffolds that occur in natural products as well as biologically active compounds. However, there is a significant gap in the current synthetic toolbox as methods to access benzonorcaradiene enantioselectively are very scarce. We disclose an enantioselective ruthenium(II)-catalyzed synthesis of benzonorcaradiene by coupling of oxabenzonorbornadienes and alkynes. An easily accessible chiral cyclopentadienyl ligand (Cp-x) provides access to exo-benzonorcaradiene in exclusive diastereoselectivity and with enantioselectivities of up to 97.5:2.5 er. Mechanistically, the transformation proceeds by a ruthenium-catalyzed part linking the alkene and alkyne moiety. This is followed by a series of pericyclic rearrangements converging to the thermodynamically favored exo-benzonorcaradiene isomer.

About this result
This page is automatically generated and may contain information that is not correct, complete, up-to-date, or relevant to your search query. The same applies to every other page on this website. Please make sure to verify the information with EPFL's official sources.
Related concepts (9)
Ruthenium
Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemicals. Russian-born scientist of Baltic-German ancestry Karl Ernst Claus discovered the element in 1844 at Kazan State University and named ruthenium in honor of Russia. Ruthenium is usually found as a minor component of platinum ores; the annual production has risen from about 19 tonnes in 2009 to some 35.
Olefin metathesis
Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds. Because of the relative simplicity of olefin metathesis, it often creates fewer undesired by-products and hazardous wastes than alternative organic reactions. For their elucidation of the reaction mechanism and their discovery of a variety of highly active catalysts, Yves Chauvin, Robert H. Grubbs, and Richard R.
Rhodium
Rhodium is a chemical element with the symbol Rh and atomic number 45. It is a very rare, silvery-white, hard, corrosion-resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isotope: 103Rh. Naturally occurring rhodium is usually found as a free metal or as an alloy with similar metals and rarely as a chemical compound in minerals such as bowieite and rhodplumsite. It is one of the rarest and most valuable precious metals.
Show more
Related publications (5)

Development of Catalytic Asymmetric C-H Functionalizations with Chiral Cyclopentadienyl Iridium(III) Complexes

Yun-Suk Jang

Cp*Ir(III) catalyzed C-H functionalization is a growing field, since it provides novel complementary reactivities, but enantioselective C-H functionalization reactions with this metal remain a niche. This thesis investigates CpXIr(III) catalyzed asymmetric ...
EPFL2019

Methane Production from Microalgae via Continuous Catalytic Supercritical Water Gasification: Development of Catalysts and Sulfur Removal Techniques

Gaël Peng

This doctoral thesis aims at demonstrating the technical feasibility of methane production from microalgae via continuous catalytic supercritical water gasification (CSCWG). This work focuses on three different research approaches: (i) assessment and impro ...
EPFL2015

Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

Paul Joseph Dyson, Gabor Laurenczy, Séverine Joëlle Moret

The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic ...
2014
Show more

Graph Chatbot

Chat with Graph Search

Ask any question about EPFL courses, lectures, exercises, research, news, etc. or try the example questions below.

DISCLAIMER: The Graph Chatbot is not programmed to provide explicit or categorical answers to your questions. Rather, it transforms your questions into API requests that are distributed across the various IT services officially administered by EPFL. Its purpose is solely to collect and recommend relevant references to content that you can explore to help you answer your questions.