39547-01-8

Upstream product

• 6142-57-0 (+/-)-trans-2-methylcyclopropanecarboxylic acid 
• 186581-53-3 diazomethane 
• 123-73-9 trans-Crotonaldehyde 
• 21003-36-1 trans-1-(hydroxymethyl)-2-methylcyclopropane 
• 6077-72-1 2-methylcyclopropanemethanol 
• 75-11-6 diiodomethane 
• 504-61-0 (E)-but-2-enol 

Relevant academic research and scientific papers

Radical-Cation Vinylcyclopropane Rearrangements by TiO2Photocatalysis

Radical cation vinylcyclopropane rearrangements by TiO2 photocatalysis in lithium perchlorate/nitromethane solution are described. The reactions are triggered by oxidative single electron transfer, which is followed by immediate ring-opening of the cyclopropanes to generate distonic radical cations as unique reactive intermediates. This approach can also be applied to vinylcyclobutane, leading to the construction of six-membered rings. A stepwise mechanism via distonic radical cations is proposed based on preliminary mechanistic studies, which is supported by density functional theory calculations.

Synthesis of azepine derivatives by rhodium-catalyzed tandem 2,3-rearrangement/heterocyclization

Easy to N-cycle: The efficient synthesis of azepine derivatives was achieved by Rh-catalyzed tandem 2,3-rearrangement involving the heterocyclization of N-allenylnitrone intermediates (see scheme; cod=1,5-cyclooctadiene, tppms=sodium diphenylphosphinobenz

Reactions of diazoalkanes with unsaturated compounds 15. Catalytic reactions of unsaturated carbonyl compounds and their derivatives with diazomethane

The present study concerned with the influence of the nature of the acetal fragment in unsaturated compounds on the reactivity of the C=C bond in cyclopropanation reactions with diazomethane catalyzed by copper and palladium compounds. The acetal substitu

A novel strategy for the asymmetric synthesis of chiral cyclopropane carboxaldehydes

A new way of combining chiral auxiliaries and substrate-directable reactions for asymmetric synthesis is described that employs a three-step sequence of aldol-cyclopropanation-retroaldol reactions for the stereoselective synthesis of enantiopure cycloprop

Thermal Ring-Expansion of N-Acyl Cyclopropyl Imines

The FVT of N-acyl cyclopropyl imines with methyl, phenyl, and acyl substituents at C-1 or C-2 of the cyclopropyl ring has been studied.The parent N-acyl cyclopropyl imine and N-acyl methylcyclopropyl imines gave no ring-expansion products but ring-opened mixtures, decomposed fragments, and polymerization tars after FVT, whereas N-acyl phenylcyclopropyl imines and N-acyl acylcyclopropyl imines generated ring-expansion products, 2-pyrrolines.It demonstrates the first study on the thermal rearrangement of N-acyl cyclopropyl imines.

Stereochemistry of the thermal isomerizations of (1/R,2R)-1-((E)-Styryl)-2-methylcyclopropane to 3-phenyl-4-methylcyclopentenes

(1A,2R)-1-((E)-Styryl)-2-methylcyclopropane at 250 °C racemizes and isomerizes to 6-phenylhexa-1,4-(Z)-diene and to the four isomers of 3-phenyl-4-methylcyclopentene. From the measured rate constants for racemization and for structural isomerizations, and

The Influence of Intramolecular Dynamics on Branching Ratios in Thermal Rearrangements

1- and 2-phenylbicyclohex-2-enes-5-d undergo thermal rearrangement to give products, differing only in the location of the deuterium, in ratio of about 9:1, but with identical activation enthalphies.Similarly, opticallly active trans-2-methyl-1-(trans-2-phenylethenyl)cyclopropane is found to rearrange to enantiomeric methylphenylcyclopentenes that are formed in a 5.9:1 ratio but with virtually identicyl activation enthalphies.Barring repeated coincidence, these results do not seem to be explicable within the framework of statistical theories of unimolecular kinetics such as RRKM theory, transition state theory, and variational transition state theory.The possible influence of dynamic effects in these and other unimolecular reactions is discussed.

Regioselectivity in the Ring Opening of 2-Alkylcyclopropylmethyl Radicals: the Effect of Electronegative Substituents

The regioselectivity of the ring-opening of the trans-2-alkylcyclopropylmethyl radical A to give the primary alkyl radicals B, or the secondary alkyl radicals C, has been investigated, where the groups R and/or CXY carry electronegative substituents.All these reactions gave principally the secondary alkyl radicals C, whereas, in the absence of electronegative substituents, ring-opening occurs in favour of the primary alkyl radicals B.This regioselectivity is interpreted in terms of the frontier orbital interactions which are involved.

Z/E-Isomerization of Unsaturated Carboxylic Acids during the Kolbe Electrolysis

Z-4-Enoic acids partially isomerize to E-configurated products in the Kolbe electrolysis.The results from methyl and deuterium labelled carboxylic acids 2 and 16 support an isomerization via a reversible ring closure to cyclopropylcarbinyl radicals.The double bonds of Z-N-enoic acids with N>/= 5 fully retain their configuration in the Kolbe electrolysis; for N=6,7 cyclic products are formed to some extent, which is in accord with the reactivity of 5- and 6-alkenyl radicals.