5723-84-2

Upstream product

• 119-61-9 benzophenone 
• 110-83-8 cyclohexene 
• 108-31-6 maleic anhydride 
• 108-86-1 bromobenzene 
• 29373-01-1 cyclohex-2-en-1-yl(phenyl)methanone 
• 1521-51-3 rac-3-bromocyclohexene 
• 822-67-3 Cyclohex-2-enol 
• 25662-37-7 methyl cyclohex-2-en-1-carboxylate 
• 100-58-3 phenylmagnesium bromide 
• 100-52-7 benzaldehyde 
• 5723-89-7 syn-3-<(Hydroxyphenyl)methyl>cyclohexene 

Relevant academic research and scientific papers

Easy access to secondary and tertiary alcoholsviametal-free and light mediated radical carbonyl allylation

Here we report a strategy for carbonyl addition with unactivated alkenes using an organic photocatalyst on both aldehyde and ketone substrates. This protocol grants us a good alternative to the traditional Barbier-Grignard allylation that exhibits poor functional group tolerance. With this method the stoichiometric use of metals can be avoided, high atom economy can be achieved and fewer by-products are generated.

Visible-Light Photoredox Enables Ketone Carbonyl Alkylation for Easy Access to Tertiary Alcohols

Being a handle for synthesizing quaternary carbon centers and olefins, together with ubiquitous appearance in organic building blocks, makes tertiary alcohols valuable targets in synthesis. However, traditional syntheses of these alcohols have faced several challenges including the employment of functionalized reactive reagents, undesirable side reactions, and decomposition of the alcohol products under harsh conditions. The paucity of a synthetic approach to bulky tertiary alcohols prompts our interest to develop a benign catalytic protocol to tackle the current issues. Here, we have successfully demonstrated the use of ketyl radicals in intermolecular cross radical-radical coupling, which has opened a different door for accessing complex tertiary alcohols. On the other hand, by starting from feedstock and naturally derived chemicals without any pre-activation, it would be superior to traditional methodologies in the industrial context.

Photocatalytic Barbier reaction-visible-light induced allylation and benzylation of aldehydes and ketones

We report a photocatalytic version of the Barbier type reaction using readily available allyl or benzyl bromides and aromatic aldehydes or ketones as starting materials to generate allylic or benzylic alcohols. The reaction proceeds at room temperature under visible light irradiation with the organic dye 3,7-di(4-biphenyl)1-naphthalene-10-phenoxazine as a photocatalyst and DIPEA as sacrificial electron donor. The proposed cross-coupling mechanism of a ketyl- and an allyl or benzyl radical is supported by spectroscopic investigations and cyclic voltammetry measurements.

Malononitrile as acylanion equivalent

The oxidation of derivatives of malononitrile with peracid in methanol proceeds with loss of the cyano groups to yield methyl esters in high yield. The method was applied to a variety of malononitrile derivatives, some of which were prepared by Pd- or Ir-catalyzed asymmetric allylic substitution. Georg Thieme Verlag Stuttgart.

The formation of 7-oxabicyclo[4.2.0]octanes and 6-oxabicyclo[3.2.1]octanes via cationic iodocyclization

Several 2-cyclohexenemethanol derivatives were subjected to cationic iodocyclization. Two product types were formed: the fused 7-oxabicyclo[4.2.0]octane, and the bridged 6-oxabicyclo[3.2.1]octane. The degree of substitution in the alkenol determined the ratio of the products, with aromatic substituents leading to the formation of the fused system as the major product.

Use of cyclic allylic bromides in the zinc-mediated aqueous Barbier-Grignard reaction

The zinc-mediated aqueous Barbier-Grignard reaction of cyclic allylic bromide substrates with various aldehydes and ketones to afford homoallylic alcohols was investigated. Aromatic aldehydes and ketones afforded adducts in good yields (66-90%) and with good diastereoselectivities. Non-aromatic aldehydes also reacted well under these conditions, but only poor yields were obtained with non-aromatic ketones. Regioselectivity was high when some substituted cyclic allylic bromides were investigated.

REDUCTIVE METALLATION A GENERAL PREPARATIVE METHOD FOR HYDROCARBON ALLYLMETALLIC COMPOUNDS

Because of the great ease of preparation of allyl phenyl sulfides and their smooth reductive lithiation using lithium naphthalenide or 1-(dimethylamino)naphthalenide, these are ideal substrates for a particularly versatile preparative method for allylic a

The use of insoluble benzoylated polystyrene beads (polymeric benzophenone) in photochemical reactions

Friedel-Crafts benzoylation of 2percent-divinylbenzene (DVB) cross-linked polystyrene beads yielded insoluble polymeric analogs of benzophenone which were used as sensitizers in the photocycloaddition of cyclohexene to maleic anhydride and in the E-Z isomerization of (E)-1,3-pentadiene and methyl (E)-2,2-dimethyl-3,5-hexadienoate.In the first reaction, the use of polymer-anchored sensitizers resulted in the separation of polymer-attached by-product by simple filtration, although the yield of photoadducts was less than three quarters of that obtained when using benzophenone itself, and the recovered polymers could not be reused.In the photoisomerizations, the compositions of the photostationary states reached when using the polymeric sensitizers (now reusable) were shown to depend on the degree of functionalization of the polymers via steric hindrance to the energy transfer process.Intrapolymerically sensitized E-Z photoisomerization was also demonstrated on a polymer containing benzophenone and diene units.Photooxidation of secondary alcohols (isopropanol, cyclohexanol) to ketones and photooxygenation of 2,3-dimethyl-2-butene to 2,3-dimethyl-3-buten-2-yl hydroperoxide (in the presence of oxygen) were other reactions for which polymeric benzophenones could be used.

PHOTOCYCLOADDITION OF CYCLOHEXENE AND MALEIC ANHYDRIDE SENSITIZED BY INSOLUBLE BENZOYLATED POLYSTYRENE

Friedel-Crafts benzoylation of styrene - 2percent DVB copolymer beads yielded insoluble benzoylated polystyrene which was successfully used as sensitizer in the photocycloaddition of cyclohexene with maleic anhydride.