Day 2 :
Keynote Forum
Don M Coltart
University of Houston, USA
Keynote: An umpolung approach to the Asymmetric -Alkylation of aldehydes and ketones
Time : 09:30-09:55
Biography:
The asymmetric alkylation of carbonyl compounds is a fundamental synthetic transformation. Remarkably, despite its importance, there is no general way to conduct this transformation in a catalytic asymmetric fashion. The umpolungbased alkylation of ketones and aldehydes wherein an organometallic species adds to an electrophilic carbon through the intermediacy of a derived azo- or nitrosoalkene provides an appealing approach to effecting this transformation. Not only does such an approach allow for the incorporation of functionality that cannot be introduced using enolate chemistry, but it is also well suited to catalysis and adaptable for asymmetric induction. Given the wide range of structures available as organometallic reagents (e.g., 1°, 2°, 3° alkyl, aryl, vinyl, alkynyl, etc.), this approach to catalytic asymmetric alkylation is also likely to prove broad in scope. Herein, we describe our recent efforts to exploit this mode of reactivity to provide a solution to the longstanding problem of developing a general, catalytic asymmetric approach to the alkylation of carbonyl compounds.
Abstract:
The asymmetric alkylation of carbonyl compounds is a fundamental synthetic transformation. Remarkably, despite its importance, there is no general way to conduct this transformation in a catalytic asymmetric fashion. The umpolungbased alkylation of ketones and aldehydes wherein an organometallic species adds to an electrophilic carbon through the intermediacy of a derived azo- or nitrosoalkene provides an appealing approach to effecting this transformation. Not only does such an approach allow for the incorporation of functionality that cannot be introduced using enolate chemistry, but it is also well suited to catalysis and adaptable for asymmetric induction. Given the wide range of structures available as organometallic reagents (e.g., 1°, 2°, 3° alkyl, aryl, vinyl, alkynyl, etc.), this approach to catalytic asymmetric alkylation is also likely to
prove broad in scope. Herein, we describe our recent efforts to exploit this mode of reactivity to provide a solution to the longstanding problem of developing a general, catalytic asymmetric approach to the alkylation of carbonyl compounds.
Keynote Forum
Alexander O Terentev
ZIOC RAS, Russia
Keynote: Oxidative cross-dehydrogenative coupling with selective C-O bond formation
Time : 09:30-09:55
Biography:
Oxidative cross-dehydrogenative coupling methodology lies in the modern trend of organic chemistry. It eliminates
necessity for installation of additional functional groups and affords direct coupling in one stage (via selective C-H
activation) with limited amount of wastes, high atom- and step- economy. Oxidative cross-dehydrogenative C-C coupling was studied in most detail; the C-N, C-P, and C-O cross-coupling reactions are less well developed. It is diffi cult to achieve high selectivity in the cross-dehydrogenative C-O coupling because the starting compounds are prone to side oxidation and fragmentation reactions giving, for example, alcohols and carbonyl compounds. This gives rise to a problem of searching for oxidizing agents and reaction conditions suitable for the cross-coupling of different types of substrates. We discovered oxidative cross-dehydrogenative C-O coupling of 1,3-dicarbonyl compounds and their heteroanalogs with peroxides, oximes and hydroxyamides. The best results were obtained with the use of the widely available copper, iron, manganese or lanthanide salts as catalysts or oxidants.
Abstract:
Oxidative cross-dehydrogenative coupling methodology lies in the modern trend of organic chemistry. It eliminates necessity for installation of additional functional groups and affords direct coupling in one stage (via selective C-H activation) with limited amount of wastes, high atom- and step- economy. Oxidative cross-dehydrogenative C-C coupling was studied in most detail; the C-N, C-P, and C-O cross-coupling reactions are less well developed. It is diffi cult to achieve high selectivity in the cross-dehydrogenative C-O coupling because the starting compounds are prone to side oxidation and fragmentation reactions giving, for example, alcohols and carbonyl compounds. This gives rise to a problem of searching for oxidizing agents and reaction conditions suitable for the cross-coupling of different types of substrates. We discovered oxidative cross-dehydrogenative C-O coupling of 1,3-dicarbonyl compounds and their heteroanalogs with peroxides, oximes and hydroxyamides. The best results were obtained with the use of the widely available copper, iron, manganese or lanthanide salts as catalysts or oxidants.
- Physical Chemistry
Environmental Chemistry
Theoretical Chemistry
Location: Linate
Chair
Goncagul Serdaroglu
Cumhuriyet University, Turkey
Co-Chair
Dorothee ARNS
Petrochemicals Europe, Belgium