14161-72-9

Upstream product

• 908094-04-2 phenyldiazomethane 
• 98-83-9 isopropenylbenzene 
• 65051-83-4 3-methyl-3-phenylcyclopropene 
• 1078-58-6 diphenylzinc 
• 98-80-6 phenylboronic acid 
• 55091-64-0 1-methyl-1-phenyl-2-bromocyclopropane 
• 63269-86-3 3-methyl-3-phenyl-3H-diazirine 
• 100-42-5 styrene 
• 98-86-2 acetophenone 
• 1896-62-4 (E)-benzalacetone 
• 22293-10-3 (1-diazoethyl)benzene 
• 7585-39-9 β‐cyclodextrin 
• 729-43-1 acetophenonazine 
• 591-50-4 iodobenzene 

Downstream Products

• 4894-24-0 3,5-diphenyl-5-methyl-4,5-dihydroisoxazole 

Relevant academic research and scientific papers

STEREOSPECIFIC CYCLOPROPANE SYNTHESIS FROM Γ-STANNYL ALCOHOLS

Tertiary and benzyl alcohols with a γ-trialkyltin group from cyclopropanes stereospecifically on treatment with acid, with inversion of configuration at both carbon atoms.

Iron-catalyzed synthesis of cyclopropanes by in situ generation and decomposition of electronically diversified diazo compounds

The modular synthesis of a variety of trans 1,2-disubstituted cyclopropanes in a safe and user-friendly one-pot iron-catalyzed cyclopropanation reaction is described. Easily synthesized N-nosylhydrazones are used as diazo precursors, allowing the in situ generation of electron-rich diazo compounds under mild reaction conditions and their direct participation in the cyclopropanation reaction.

Rhodium-Catalyzed Arylation of Cyclopropenes Based on Asymmetric Direct Functionalization of Three-Membered Carbocycles

A variety of highly diastereo- and enantiomerically enriched arylcyclopropanes is obtained through the asymmetric rhodium-catalyzed arylation reaction of achiral nonfunctionalized cyclopropene derivatives with commercially available aryl boronic acids in the presence of (R,S)-Josiphos.

Asymmetric Copper-Catalyzed Carbozincation of Cyclopropenes en Route to the Formation of Diastereo- and Enantiomerically Enriched Polysubstituted Cyclopropanes

The enantioselective synthesis of cyclopropylzinc reagents has been achieved via a copper-catalyzed carbozincation of 3,3-disubstituted cyclopropenes with diorganozinc reagents. The obtained organozinc compounds can be easily functionalized with a broad range of electrophiles, including palladium-catalyzed cross-couplings, affording highly substituted cyclopropanes. The operationally simple procedure using very low quantities of a commercially available and inexpensive copper catalyst provides a new tool for the synthesis of highly enantioenriched cyclopropanes as single diastereoisomers.

Copper-catalyzed diastereo- and enantioselective desymmetrization of cyclopropenes: Synthesis of cyclopropylboronates

A novel Cu-catalyzed diastereo- and enantioselective desymmetrization of cyclopropenes to afford nonracemic cyclopropylboronates is described. Trapping the cyclopropylcopper intermediate with electrophilic amines allows for the synthesis of cyclopropylaminoboronic esters and demonstrates the potential of the approach for the synthesis of functionalized cyclopropanes.

Improved zinc-catalyzed simmons-smith reaction: Access to various 1,2,3-trisubstituted cyclopropanes

The Simmons-Smith reaction of zinc carbenoids with alkenes is a powerful method to access cyclopropanes containing various substitution patterns. This work exploits the high reactivity of aryldiazomethanes toward zinc halides to generate aryl-substituted carbenoids catalytically. These carbenoids are able to cyclopropanate various alkenes diastereoselectively, including unfunctionalized substrates such as styrenes. The zinc catalyst can be modified to tolerate the use of free allylic alcohols.

Electronically tuned chiral ruthenium porphyrins: Extremely stable and selective catalysts for asymmetric epoxidation and cyclopropanation

We report the use of three enantiomerically pure and electronically tuned ruthenium carbonyl porphyrin catalysts for the asymmetric cyclopropanation and epoxidation of a variety of olefinic substrates. The D4-symmetric ligands carry a methoxy, a methyl or a trifluoromethyl group at the 10-position of each of the 9-[anti-(1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene)]-substituents at the meso-positions of the porphyrin. Introduction of a CF 3-substituent in this remote position resulted in greatly improved catalyst stability, and turnover numbers of up to 7500 were achieved for cyclopropanation, and up to 14200 for epoxidation, with ee values typically >90% and ≈80%, respectively. In one example, the axial CO ligand at the ruthenium was exchanged for PF3, resulting in the first chiral ruthenium porphyrin with a PF3 ligand reported to date. In cyclopropanations with ethyl diazoacetate, the latter catalyst performed exceedingly well, and gave a 95% ee in the case of 1,1-diphenylethylene as substrate.

Catalytic cyclopropanation of alkenes using diazo compounds generated in situ. A novel route to 2-arylcyclopropylamines

(Equation presented) A user-friendly, one-pot process for catalytic cyclopropanation of alkenes from tosylhydrazones is described. The cyclopropanation of N-vinylphthalimide provides a new route to 2-arylcyclopropylamines, and this is exemplified in the efficient synthesis of the HIV-1 reverse transcriptase inhibitor 6.

COMPLEXES OF CYCLOMALTOHEPTAOSE WITH AROMATIC DIAZO COMPOUNDS: FORMATION AND REACTIONS

Pyrolysis of the relatively stable, solid complexes of cyclomaltoheptaose (β-cyclodextrin) with phenyldiazomethane, 1-diazo-1-phenylethane, and diazo(diphenyl)methane results in degradation of the labile guests.The host matrix exerts "reaction-vessel" and "shape-selectivity" effects upon the reaction pathways of the guests and derivatives.The carbene insertion reaction with the β-cyclodextrin hydroxyl groups is regioselective.

β-Cyclodextrin as a Molecular Reaction Vessel: Reactions of Included Phenylmethyldiazirine

Phenylmethyldiazirine forms a stable, solid complex with β-cyclodextrin.The diazirine was decomposed by pyrolysis or irradiation of the complex, and the reaction products were analyzed.The major volatile products consist of the isomeric 1,2-diphenyl-1-methylcyclopropanes.Under photolytic conditions a significant amount of styrene also is formed.The selectivity for trans isomer formation is 10 times greater from the CD complex than from the neat state.Carbene insertion products with β-cyclodextrin are formed under both reaction conditions.The product distributions are explained by cage and shape-selective effects exerted by β-cyclodextrin.