Organometallic and inorganic synthesis for the development of new strategies for oxidation chemistry. Investigation of the structures of reactive intermediates and the effects of confinement and proximity on organic reactions.
N2 - Ammonium analogues 5 and 7 of the primary (2) and tertiary (3) cyclopropylcarbinyl cations, respectively, proposed as reactive intermediates in the enzyme-catalyzed rearrangement of presqualene diphosphate (1) to squalene (4), were synthesized. The general strategy involved construction of the appropriately substituted cyclopropanecarboxylic acids and introduction of the amino groups by a Curtius rearrangement. When the isocyanates from the Curtius reaction were trapped with (trimethylsilyl)ethanol, the resulting carbamates were easily cleaved with fluoride ion to give excellent yields of the corresponding cyclopropylamines. Amino acid 6, an analogue of the primary cyclopropylcarbinyl cation-pyrophosphate ion pair generated during the initial step of the rearrangement, was prepared by tethering a phosphonophosphate moiety to the amino group in 5 by a three-carbon bridge.
Reactive Intermediates in Organic Chemistry - Rakuten …
AB - An efficient synthesis of spiro-fused macrolactams by a multicomponent macrocyclization reaction (MCMR) is reported. The use of highly reactive, transient intermediates in this MCMR permits short reaction times, even at high dilution. The methods employed for this MCMR were first developed as a four-component strategy for the synthesis of β-ketoamide isoxazolines and a new macrocyclization reaction is reported.
organic reactive intermediates | Download eBook pdf, …
The purpose of this paper is to outline a logical presentation of the more important reactive intermediates the student is likely to encounter in organic chemistry.
examples illustrating their use in organic synthesis.
An efficient synthesis of spiro-fused macrolactams by a multicomponent macrocyclization reaction (MCMR) is reported. The use of highly reactive, transient intermediates in this MCMR permits short reaction times, even at high dilution. The methods employed for this MCMR were first developed as a four-component strategy for the synthesis of β-ketoamide isoxazolines and a new macrocyclization reaction is reported.
Sulfur-Centered Reactive Intermediates in Chemistry and ..
Inorganic and materials chemistry, focusing on design and synthesis of metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) applied to energy-related research (e.g., CO2 capture, H2 storage), catalysis, and biomedical applications.
Reactive Intermediates In Organic Chemistry Structure …
Electrochemistry serves as a powerful method for generating reactive intermediates, such as organic cations. In general, there are two ways to use reactive intermediates for chemical reactions: (1) generation in the presence of a reaction partner and (2) generation in the absence of a reaction partner with accumulation in solution as a “pool” followed by reaction with a subsequently added reaction partner. The former approach is more popular because reactive intermediates are usually short-lived transient species, but the latter method is more flexible and versatile. This review focuses on the latter approach and provides a concise overview of the current methods for the generation and accumulation of cationic reactive intermediates as a pool using modern techniques of electrochemistry and their reactions with subsequently added nucleophilic reaction partners.
Organic Reactive Intermediates by Samuel P. McManus …
Undergraduates will find Reactive Intermediates an invaluable summary of this important topic in organic chemistry--one that fills a gap created by the superficial treatment accorded these valuable compounds in most chemistry textbooks.