A facile regioselective construction of spiro epoxy-bridged tetrahydropyranone frameworks

Investigations on the reactivity profile of the transient five-membered-ring cyclic carbonyl ylides, generated from alpha-diazo ketones, in the presence of the C=O group of various simple ketones and symrnetrical/unsymmetrical 1,2-diones were carried out. The reaction of alpha-diazo ketones with 1,2-naphthoquinone furnished interesting diastereomeric cycloadducts in which both the C=O groups acted as dipolarophilic sites. The similar reaction in the presence of several isatin derivatives afforded novel spiro dioxa-bridged indole derivatives as a mixture of diastereomers. The single crystal X-ray structure analysis manifestly revealed the mode of cycloaddition and the stereochemistry of two of the diastereomers. A diverse set of novel spiro epoxy-bridged tetrahydropyranone frameworks have been constructed in good yield via the tandem cyclization-cycloaddition of alpha-diazo ketones with the C=O group as heterodipolarophile in a regioselective manner. (C) 2003 Elsevier Ltd. All rights reserved.

Electronic Control of Facial Selection in Additions to Sterically Unbiased Ketones and Olefins

By definition, the two faces of a pi bond are equivalent.1 However, they are rendered nonequivalent in most molecules because of the absence of a plane of symmetry encompassing the double bond and the adjacent substituents. As a result, additions to trigonal centers from the two faces need not be equally facile. Exploiting this stereodifferentiation in a controlled manner represents one of the core problems in organic synthesis. Evidently, the factors which determine such diastereoselection need to be delineated in as much detail as possible.

A Simple and Convenient One Step Method for the Reductive Deoxygenation of Aryl Ketones to Hydrocarbons

A one step, clean and efficient, conversion of arylaldehydes, ketones and ketals into the corresponding hydrocarbon using ionic hydrogenation conditions employing sodium cyanoborohydride in the presence of two to three equivalents of BF3. OEt(2) is described.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Oxidations of thio ketones by singlet and triplet oxygen

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutylth ioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradid peroxide is believed to be a common primary intermediate for both sulfine and ketone. Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate. Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2. Singlet oxygen is also generated through energy transfer from the triplet state of thioketones. These excited states also directly react with oxygen to yield ketone.

Oxidations of thio ketones by singlet and triplet oxygen

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutylth ioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradid peroxide is believed to be a common primary intermediate for both sulfine and ketone. Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate. Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2. Singlet oxygen is also generated through energy transfer from the triplet state of thioketones. These excited states also directly react with oxygen to yield ketone.

The perturbational treatment of the process of hydrogen abstraction by ketones

The change in energy during hydrogen abstraction by ketones is estimated for different electronic states as a function of the intermolecular orbital overlap employing perturbation theory. The results suggest that ketones preferentially undergo the in-plane reaction and abstract a hydrogen atom in their triplet nπ* state. For ketones where the triplet ππ* state lies below the triplet nπ* state, hydrogen abstraction can take place in the ππ* state owing to the crossing of the zero order reaction surfaces of the nπ* and ππ* states.

Role of barriers to conformational changes in ketones undergoing the Norrish type II process

The Norrish type II process is examined in three ketones containing primary, secondary and tertiary C---H bonds in the γ position relative to the carbonyl groups; the MINDO/3 semiempirical self-consistent field (SCF) molecular orbital (MO) method was used with complete geometry optimization in the unrestricted Hartree—Fock frame for the open-shell species. Results show that barriers to conformational change in ketones play an important role in the triplet reaction.

The Mechanism Of The Hydrogen Abstraction Process By Photo-Excited Ketones

Qualitative potential energy surfaces for hydrogen abstraction from alkanes containing primary, secondary and tertiary C-H bonds by a photo-excited ketone have been reported, The results suggest that the activation barriers for these processes decrease in the order primary > secondary > tertiary in agreement with the observed trend in the rate constants. The analysis of the electronic structure of the transition-state reveal that electron-transfer from hydrocarbon to ketone and formation of a new bond are almost synchronous in the hydrogen transfer process. The tunneling of hydrogen is not important in the normal temperature region even though the barriers are small.

Acid-Catalyzed Thermal Rearrangement of Gamm,Delta-Unsaturated Ketones

Thermal activation of gamma,delta-unsaturated ketones (1, 9 and 12) in the presence of a catalytic amount of propionic acid causes a rearrangement to give new gamma,delta-unsaturated ketones (2, 10 and 14) via an intramolecular ene reaction followed by a retro-ene reaction.