70681-91-3

Upstream product

• 31502-25-7 (E)-6-bromohex-2-ene 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 60653-76-1 <(E)-4-Hexenyl>-methansulfonat 
• 928-93-8 4-hexyn-1-ol 
• 928-92-7 (E)-hex-4-en-1-ol 
• 3003-84-7 Tetrahydrofurfuryl chloride 
• 86840-58-6 3-<(Z)-4-hexenyl>-2-cyclohexen-1-one 
• 62614-70-4 trans-1-chlorohex-4-ene 

Downstream Products

• 70681-89-9 ((E)-3-Hex-4-enyl)-cyclohex-2-enol 

Relevant academic research and scientific papers

Intramolecular [2+2] Photocycloaddition of Cyclic Enones: Selectivity Control by Lewis Acids and Mechanistic Implications

The intramolecular [2+2] photocycloaddition of 3-alkenyl-2-cycloalkenones was performed in an enantioselective fashion (nine representative examples, 54–86 % yield, 76–96 % ee) upon irradiation at λ=366 nm in the presence of an AlBr3-activated oxazaborolidine as the Lewis acid. An extensive screening of proline-derived oxazaborolidines showed that the enantioface differentiation depends strongly on the nature of the aryl group at the 3-position of the heterocycle. DFT calculations of the Lewis acid–substrate complex indicate that attractive dispersion forces may be responsible for a change of the binding mode. The catalytic [2+2] photocycloaddition was shown to proceed on the triplet hypersurface with a quantum yield of 0.05. The positive effect of Lewis acids on the outcome of a given intramolecular [2+2] photocycloaddition was illustrated by optimizing the key step in a concise total synthesis of the sesquiterpene (±)-italicene.

Regiochemistry and Stereochemistry of Intramolecular Photocycloaddition of Carbon-Carbon Double Bonds to Cyclohexenones

The intramolecular photocycloaddition mechanism of alkenes tethered by a three-methylene chain to cyclohexenones has been studied.It was found that the reversion from a 1,4-diradical intermediate to starting material is slow relative to the rate of photoadduct formation.Only "straight" closure was observed in the systems studied.For compounds 1-3 and 5, the assumption that the first bond is formed between the β-carbon of the enone and C-4' leading to a 1,4-diradical is supported.For the formation of compounds 6-11, possible mechanisms are discussed.

Intramolecular Photocycloadditions of E and Z Olefins to Cyclohex-2-enone

The intramolecular photocycloaddition of E and Z olefins to a cyclohexenone has been investigated; it is concluded that the bond to C(3) in the cyclohexenone is formed first to give the diradical intermediates (7a) and (7b).