Asymmetric Phase-Transfer Cyclization Reactions

Shibata and coworkers [135] described the asymmetric phase-transfer catalytic synthesis of trifluoromethyl-substituted 2-isoxazolines 100 by an enantioselective conjugate addition of hydroxylamine to trifluoromethylated enones 99 and subsequent intramolecular formation of the imine, whereas Briere et al. [136] developed a facile method for the straightforward enantioselective synthesis of 3,5-diaryl pyrazoHnes 102 by phase-transfer-catalyzed conjugate addition of N-Boc-hydrazine 

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This compilation embraces a wide variety of subjects, such as solid-phase and microwave stereoselective synthesis asymmetric phase-transfer asymmetric catalysis and application of chiral auxiliaries and microreactor technology stereoselective reduction and oxidation methods stereoselective additions cyclizations metatheses and different types of rearrangements asymmetric transition-metal-catalyzed, organocatalyzed, and biocatalytic reactions methods for the formation of carbon-heteroatom and heteroatom-heteroatom bonds like asymmetric hydroamina-tion and reductive amination, carboamination and alkylative cyclization, cycloadditions with carbon-heteroatom bond formation, and stereoselective halogenations and methods for the formation of carbon-sulfur and carbon-phosphorus bonds, asymmetric sulfoxidation, and so on. 

The Darzens reaction (tandem aldol-intramolecular cyclization sequence reaction) is a powerful complementary approach to epoxidation (see Chapter 5) that can be used for the synthesis of a,P-epoxy carbonyl and a,p-epoxysulfonyl compounds (Scheme 8.32). Currently, all catalytic asymmetric variants of the Darzens reactions are based on chiral phase-transfer catalysis using quaternary ammonium salts as catalysts. 

In the presence of cinchona derivatives as catalysts, peroxides or hypochlorites as Michael donors react with electron-deficient olefins to give epoxides via conjugate addition-intramolecular cyclization sequence reactions. Two complementary methodologies have been developed for the asymmetric epoxidation of electron-poor olefins, in which either cinchona-based phase-transfer catalysts or 9-amino-9(deoxy)-epi-dnchona alkaloids are used as organocatalysts. Mechanistically, in these two... 

Other reactions described, with varying degrees of success, have been chiral epoxidation, chiral hydrogenation, chiral iodination, and chiral reduction of keto-groups. One of the last reactions is especially interesting in using a chiral phase-transfer catalyst. Finally, Johnson and his co-workers have reported in full the asymmetric induction in their steroid synthesis via polyene cyclization [e.g. (46) (47) with ca. 90 % optical purity]. ... 

Instead of using chloramine-T (pKa 13.5), the employment of more nucleophilic chloramine salt, A-chloro-A-sodiobenzyloxycarbamate (pKa 15.3), allows for an efficient aziridination of electron-deficient olefins (Michael acceptors) in the presence of a solid-liquid phase-transfer catalyst (Scheme 2.38) [57]. The reaction would involve an ionic pathway where the Michael-addition of chloramine salt to alkenes and the following back-attack of the resulting enolate at the electrophilic N-center to cyclize. This reaction was successfully extended to the asymmetric aziridination of the enones that have an auxiliary, to produce chiral aziridines with good enantioselectivities up to 87% ee. Another option to aziridinate electron-deficient alkenes is the utilization of... 

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