167151-30-6

Upstream product

• 100-52-7 benzaldehyde 
• 4039-82-1 Benzyl propargyl ether 
• 1362100-83-1 (+/-)-1-benzyloxy-2-(1H-tetrazol-5-yl)propan-2-ol 
• 1362100-71-7 (+/-)-2-(1-allyl-1H-tetrazol-5-yl)-1-benzyloxypropan-2-ol 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 197155-21-8 methallyl 1-phenylallyl ether 

Downstream Products

• 39517-83-4 4-methyl-2-phenylfuran 

Relevant academic research and scientific papers

Alkylidenecarbenes from 1,1-Dihalogenoalkenes with Samarium Diiodide: Mild and Efficient Method for the Synthesis of Cyclopentenes

A new mild method for construction of cyclopentenes via 1,5-C-H insertion of alkylidenecarbenes by the reaction of 2,2-dialkyl-1,1-dihalogenoalkenes with SmI2 in benzene-hexamethylphosphoric triamide (HMPA) was developed.

Chemo-Enzymatic Metathesis/Aromatization Cascades for the Synthesis of Furans: Disclosing the Aromatizing Activity of Laccase/TEMPO in Oxygen-Containing Heterocycles

The unprecedented Trametes versicolor laccase/TEMPO-catalyzed aromatization of 2,5-dihydrofurans to furans is described. A variety of furan derivatives have been synthesized in moderate to high conversions (21-99%) and yields (20-76%) under mild reaction

Synthesis of five-membered unsaturated compounds from ketones via cyanophosphates under neutral conditions: [1,5]-C–H insertion of alkylidene carbenes generated by tetrazole fragmentation

Cyanophosphates (CPs) can easily be prepared via the reactions of carbonyl compounds with diethyl phosphorocyanidate (DEPC) in the presence of LiCN (cat.) under non-aqueous conditions. Treatment of ketone-derived CPs with TMSN3/Bu2Sn

RUTHENIUM POLYMERISATION CATALYSTS

Cis and trans ruthenium complexes that can be used as catalysts for ring opening metathesis polymerisation (ROMP) are described. The complexes are generally square pyramidal in nature, having two anionic ligands X. Corresponding cationic complexes where one or both of the anionic ligands X are replaced by a non-co-ordinating anionic ligand are also described. Polymers such as polydicyclopentadiene (PDCPD) can be prepared using the catalysts.

Dehydrative fragmentation of 5-hydroxyalkyl-1 h -tetrazoles: A mild route to alkylidenecarbenes

The development of a mild, base-free method for the generation of alkylidenecarbenes is reported. Treatment of 5-hydroxyalkyl-1H-tetrazoles with carbodiimides generates products arising from the 1,2-rearrangement or [1,5]-C-H bond insertion of a putative alkylidenecarbene. Formation of this divalent intermediate is proposed to occur by way of a tetraazafulvene, which undergoes extrusion of 2 mol of dinitrogen. Details of this methodology, its application to the synthesis of combretastatin A-4, and an improved route to 5-hydroxyalkyl-1H-tetrazoles are described.

RUTHENIUM COMPLEXES FOR USE IN OLEFIN METATHESIS

Cis ruthenium complexes that can be used as catalysts are described. The complexes are generally square pyramidal in nature, having two anionic ligands X adjacent to each other. The complexes can be used as catalysts, for example in olefin metathesis reactions. Corresponding trans ruthenium complexes are also described, together with cationic complexes where one or both of the anionic ligands X are replaced by a non- co-ordinating anionic ligand.

Synthesis of conjugated γ- and δ-lactones from aldehydes and ketones via a vinylation(allylation)-ring closing metathesis-oxidation sequence

Nucleophilic C-vinylation and C-allylation of aldehydes and ketones followed by O-allylation of the obtained carbinols gave the corresponding allyl or homoallyl ethers, respectively. Ring-closing metathesis of these compounds afforded in many cases cyclic ethers (dihydrofurans and dihydropyrans, respectively) bearing disubstituted and trisubstituted C=C bonds. These were then subjected to allylic oxidation to yield conjugated γ- and δ-lactones. Reasons for the observed failures are presented and discussed.

Synthesis of conjugated γ- and δ-lactones from aldehydes and ketones via a vinylation/allylation-ring closing metathesis-oxidation sequence

Nucleophilic C-vinylation or C-allylation of aldehydes and ketones followed by O-allylation of the obtained carbinols gave the corresponding allyl ethers. Ring-closing metathesis of the latter afforded cyclic ethers (dihydrofurans and dihydropyrans, respectively) which were then subjected to allylic oxidation to yield conjugated γ- and δ-lactones.

Effects of Olefin Substitution on the Ring-Closing Metathesis of Dienes

Ruthenium alkylidene 1 and molybdenum alkylidene 2 have been utilized in the ring-closing metathesis (RCM) of dienes containing gem-disubstituted olefins to yield tri- and tetrasubstituted cyclic olefins. Dienes with sterically demanding and/or electron-withdrawing substituents such as Ph, CO2Me, and tBu were cyclized successfully with 2, but did not cyclize with 1. Tetrasubstituted cyclic olefins could be formed with 2, but not using alkylidene 1. Dienes with allylic functional groups yielded functionalized cyclic olefins when treated with 1.