Investigation of the Transition-Metal- and Acid-Catalyzed Reactions of β-(N-Tosyl)amino Diazo Carbonyl Compounds
TL;DR: It was found that, in most cases, the diazo decomposition gave preferentially 1, 2-aryl migration product, but 1,2-hydride migration predominated when PhCO(2)Ag/Et(3)N was the catalytic system.
Abstract: A series of β-(N-tosyl)amino diazo carbonyl compounds have been prepared by nucleophilic condensation of N-tosylimines with acyldiazomethanes. The diazo decomposition of these diazo carbonyl compounds under various catalytic conditions, including Rh(II) carboxylates, Cu(I) and Cu(II) complexes, PhCO2Ag/Et3N, TsOH, and SnCl2·2H2O, has been investigated. It was found that, in most cases, the diazo decomposition gave preferentially 1,2-aryl migration product, but 1,2-hydride migration predominated when PhCO2Ag/Et3N was the catalytic system. Hammett correlation has been applied in the analysis of the electronic effects of 1,2-aryl migration. The factors that govern the migratory preference and the mechanistic aspects of the reaction are discussed.
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TL;DR: New developments of various reactions of α-diazocarbonyl compounds have been reviewed in this article, which primarily focuses on the literatures published since 2003, focusing on the literature published in 2003.
637 citations
TL;DR: This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters.
Abstract: This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.
220 citations
TL;DR: The nucleophilic addition reaction of diazo-compound derived anions or enolates with electrophilic C=O and C=N bonds have been summarized and diverse reactivities of the diazocarbonyl compounds bearing other functional groups are demonstrated.
209 citations
TL;DR: The first visible-light induced cross-dehydrogenative coupling between tertiary amines and diazo compounds is described, successfully employed for the synthesis of 4- or 5-ester N-aryl-2,3-dihydrobenzo[d]azepines with high regioselectivity simply switched by the selection of the transition metal catalysts.
92 citations
TL;DR: Eight- and 9-membered dioxazocines and dioxazonines are readily synthesized starting from N-sulfonyl-1,2,3-triazoles in a single-step procedure and a perfect regioselectivity and generally good yields are obtained under dirhodium catalysis.
86 citations
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TL;DR: The Hammett equation has been widely used for the study and interpretation of organic reactions and their mechanisms as mentioned in this paper, and it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution.
Abstract: The Hammett equation (and its extended forms) has been one of the most widely used means for the study and interpretation of organic reactions and their mechanisms. Although the Hammett methodology has been criticized by theoreticians because of its empirical foundation, it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution. Almost every kind of organic reaction has been treated via the Hammett equation, or its extended form. The literature is so voluminous and extensive that there is no complete review of all that has been accomplished. Hammett's success in treating the electronic effect of substituents on the rates and equilibria of organic reactions1P2 led Taft to apply the same principles to steric and inductive and resonance effects? Then, more recently, octanol/ water partition coefficients (P) have been used for rationalizing the hydrophobic effects of organic compounds interacting with biological systems? The use of log P (for whole molecules) or n (for substituents), when combined with electronic and steric parameters, has opened up whole new regions of biochemical and pharmacological reactions to study by the techniques of physical organic chemistry.sf3 The combination of electronic, steric, hydrophobic, hydrophilic, and hydrogen-bonding7 parameters has been used to derive quantitative structure-activity relationships (QSAR) for a host of interactions of organic compounds with living systems or parts thereof. The binding of organic compounds to proteins,8 their interaction with enzymess and with cellsloJ1 and tiasues,12 their inhibition of organelles,l' and as antimalarial^'^
6,870 citations
TL;DR: Les aldehydes sont convertis efficacement en β-cetoesters par additon de diazoacetate d'ethyle in presence of chlorure de zinc(II) as discussed by the authors.
Abstract: Les aldehydes sont convertis efficacement en β-cetoesters par additon de diazoacetate d'ethyle en presence de chlorure de zinc(II)
272 citations
TL;DR: In this paper, carboxylate and carboxamide ligands on dirhodium (II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetates esters.
Abstract: Carboxylate and carboxamide ligands on dirhodium (II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetates esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms γ-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhoduim(II) tetrakis (perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection
247 citations
TL;DR: A comprehensive review of the chemistry of N-sulfonyl imines is presented in this paper with particular emphasis on their applications in stereoselective processes, along with a survey of their uses in a wide range of addition, pericyclic and cycloaddition reactions.
Abstract: Until recently, N-sulfonyl imines had found only limited and sporadic use in organic synthesis. During the past decade, however, it has become increasingly clear that these species are valuable synthons and are capable of undergoing many unique transformations. A comprehensive review of the chemistry of these compounds is presented here with particular emphasis on their applications in stereoselective processes. Methods for preparing N-sulfonyl imines are outlined, along with a survey of their uses in a wide range of addition, pericyclic and cycloaddition reactions.
126 citations