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.

A radical cyclisation based strategy to cuparenoids; synthesis of (±)-α-cuparenone, (±)-epilaurene and laurenes

Mercuric acetate catalysed one pot Claisen rearrangement of the cinnamyl alcohol Image , generated the pent-4-enal Image , which on homologation resulted the hex-5-enal Image . Radical cyclisation of the radical anion derived from Image , followed by oxidation provided the ketone mixture Image , a known precursor to the sesquiterpenes (Image )-α-cuparenone (Image ), (Image )-epilaurene (Image ) and laurene (Image )

One pot synthesis of polycyclic oxygen aromatics. Part IV reaction of THP ether of 2-bromomethyl phenols

Reaction of 2-bromomethyl-1-(2′-tetrahydropyranyloxy) benzene 3a with tetrachlorocatechol(TCC) in acetone in presence of anhydrous K2CO3 resulted in the formation of diastereomeric products to which cis- & trans- 6-chloro-8-hydroxy-8-(2-oxopropyl)spiro[9H-benzo[a]xanthen- 9,2′(1′H) benzofuran]-7(8H)-one (7a & 8a) structures were assigned, along with tetrachlorocatechol ethers (5a & 6a). Similar reaction of 3a with tetrabromocatechol(TBC) gave the expected monobromo compounds 7d & 8d along with the ethers 5d & 6d. When the reaction was repeated with substrates 3b–c with TCC/TBC in ketonic solvents(acetone/methyl ethyl ketone), the corresponding compounds 5b–c to 8b–c, 5e–f to 6e–f, 7e–g & 8e–h were obtained. A suitable explanation has been given for the formation of acetonyl compound 6 in this reaction.

Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor

The details of the first total synthesis of a natural thapsane lg containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) '5 described. The Claisen rearrangement of 9 with methoxypropene in the presence of a catalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of a-diazo-&keto ester 12, obtained from 10 via 8-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:l mixture of hydrindanone 6 and keto1 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane

Synthesis Based on Cyclohexadienes .11. A A new total synthesis of (±)-norprezizanone

Acid catalyzed rearrangement of endo 1-methoxytricyclo[6.2.2.0(3,8)]dodec-2-en-10-ol 8c afforded the ketone 9 which has been transformed into (+/-)-norprezizanone 19 thus completing a formal synthesis of (+/-)-zizaene. A key step in this strategy is a stereospecific 1,4-addition of a methyl group

Synthesis of (±)-thaps-7(15)-ene and (±)-thaps-6-enes

The synthesis of (±)-3a,4,4,7a-tetramethylhydrindan-2-one 8, containing three contiguous quaternary carbons as present in thapsanes, and the total synthesis of thaps-7(15)-ene 6 and thaps-6-ene 7, probable biogenetic precursors of thapsanes, have been achieved. Thus, orthoester Claisen rearrangement of cyclogeraniol 14, followed by hydrolysis of the resultant ester 16 furnished the eneacid 13. Copper sulfate-catalysed intramolecular cyclopropanation of the diazo ketone 18, derived from the acid 13, generated the cyclopropyl ketone 12. Regiospecific reductive cleavage of cyclopropyl ketone 12 furnished the hydrindanone 8, whereas the diazo ketone 26 furnished the hydrindanone 28avia the cyclopropyl ketone 27. Wittig methylenation of the hydrindanone 28a furnished thaps-7(15)-ene 6, which on isomerisation gave thaps-6-ene 7. Allylic oxidation of thaps-6-ene furnished the thapsenone 31, a degradation product of the natural thapsane 1b.

Formal total synthesis of (+)-didemniserinolipid B

The formal total synthesis of (+)-didemniserinolipid B, a marine tunicate possessing a 6,8-dioxabicyclo3.2.1]octane framework, was accomplished starting from L-(+)-tartaric acid. The key transformations in the synthesis include the elaboration of a gamma-hydroxy-amide readily obtained by desymmetrization of tartaric acid bis-amide via the controlled addition of a Grignard reagent followed by stereoselective reduction of the resulting ketone. (C) 2010 Elsevier Ltd. All rights reserved.

Pulsed laser deposition film of a donor-acceptor-donor polymer as possible active layer in devices

A molecule having a ketone group between two thiophene groups was synthesized. Presence of alternating electron donating and accepting moieties gives this material a donor-acceptor-donor (DAD) architecture. PolyDAD was synthesized from DAD monomer by oxidative polymerization. Device quality films of polyDAD were fabricated using pulsed laser deposition technique. X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectra (FTIR) data of both as synthesized and film indicate the material does not degrade during ablation. Optical band gap was determined to be about 1.45 eV. Four orders of magnitude increase in conductivity was observed from as synthesized to pulsed laser deposition (PLD) fabricated film of polyDAD. Annealing of polyDAD films increase conductivity, indicating better ordering of the molecules upon heating. Rectifying devices were fabricated from polyDAD, and preliminary results are discussed.

Chiral Synthons from Carvone. Part 10. Synthesis of (+)-(1S,3S,4S,7S, 8R)-5,7-Dimethyl-10-oxatetracyclo-(5.3.0.03,5,04,8)decan-9-one.

Degradation of the tolyl group in the tricyclic ketone 1b followed by stereospecific reduction of the resultant ketoester (6) furnishes the title compound (4) containing a new tetracyclic framework, establishing the stereochemistry of the aryl group in 1.

Dynamic structure of charge carrier in polyaniline by near-infrared excited resonance Raman spectroscopy

New vibrational Raman features characteristic to the conductive form of polyaniline have been observed with the near-infrared excitation at 1047 nm. Based on an analogy with the resonance Raman spectrum of Michler's ketone in the lowest excited triplet (T-1) state, we consider these features as due to a dynamic structure of a diimino-1,4-phenylene unit in the polyaniline chain exchanging a positive charge very rapidly. This consideration directly leads to a conducting mechanism in which a positive charge migrates from one nitrogen to the other through the conjugated chain of polyaniline.

Utility of microbes in organic-synthesis - selective transformations of acyclic isoprenoids by aspergillus-niger

Bioconversion of acyclic isoprenoids using a strain of Aspergillus niger results in hydroxylated metabolites with regio- and stereoselectivity. The organism carries out oxidation of the terminal allylic methyl group and the remote double bond in all the compounds tested (I-VII). However, these two activities seem to have preferential structural requirements. When an acyclic isoprenoid with a ketone functionality such as geranylacetone is used as the substrate, the organism also carries out the asymmetric reduction of the keto group. All the metabolites formed have been purified and characterized by conventional spectroscopic methods and quantification has been made by gas chromatographic analyses.

The Reaction of a Nitro-Capped Cobalt(III) Cage Complex With Base: the Crystal Structure of a Contracted Cage Complex, and the Mechanism of Its Formation

The synthesis, properties and crystal structure of the cage complex (1-hydroxy-8-methyl-3,6,10,13,15,18-hexaazabicyclo[6.6.5]nonadecane)cobalt(III) chloride hydrate ([Co(Me,OH-absar)] C13.H2O) are reported. The mechanism of the formation of this contracted cavity cage from a nitro-capped hexaazabicycloicosane type cage has been investigated. Treatment of (1-methyl-8-nitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) chloride ([Co(Me,NO2-sar)] 3+) with excess base in aqueous solution leads initially to rapid (t1/2 < 1 ms) and reversible deprotonation of one coordinated secondary amine. This species undergoes a retro-Mannich type reaction and imine hydrolysis (t1/2 almost-equal-to 90 s). Quenching the reaction with acid gives rise to a pair of isomeric intermediate species which have been isolated and characterized. They have a pendant arm macrocyclic structure, resulting from the loss of a methylene unit from one of the arms of the cap. Heating either isomer in aqueous solution gives the new cage compound with the contracted cap. It is postulated that this occurs through a Nef reaction, resulting in the formation of a ketone which then condenses with the coordinated primary amine. A comparison with the corresponding bicycloicosane analogue indicates a reduced chromophoric cavity size for the contracted cage. The reduction potential of the cobalt(III)/cobalt(II) couple is 170 mV more negative for the smaller cage, and, in the electronic spectrum of the cobalt(III) complex, the d-d transitions are both shifted to higher energy, corresponding to a stronger ligand field.

Total synthesis of (±)-allo-cedrol [Khusiol]

The first total synthesis of (+/-)-allo cedrol 1 is described from the ketone 11 which involves the Lewis acid catalysed rearrangement of the prezizaene analogue 8 as the key step.

Stereospecific construction of stereogenic vicinal quaternary carbon atoms. Enantiospecific synthesis of (+)-valerane

Stereo- and enantiospecific synthesis of (+)-valerane starting from R-carvone utilising orthoester Claisen rearrangement and intramolecular diazo ketone cyclopropanation reactions for the construction of the two vicinal quaternary carbon atoms is described. Copyright (C) 1996 Elsevier Science Ltd.

Synthetic approaches to homogynolides A and B

A four step, efficient and general methodology for the conversion of a cyclic ketone into the corresponding alpha-spiro-beta-methylene-gamma-butyrolactone, the key structural feature present in tricyclic sesquiterpenes bakkanes, has been developed employing a regiospecific 5-exo dig radical cyclisation reaction as the key step. The methodology has been extended to the total synthesis of bakkanes including homogynolide-B and chiral homogynolide-A.