65051-84-5

Upstream product

• 52178-73-1 1-(2,2-dibromo-1-methylcyclopropyl)-4-methoxybenzene 
• 1712-69-2 1-isopropenyl-4-methoxybenzene 
• 65051-82-3 1-bromo-2-p-anisyl-2-methylcyclopropane 

Relevant academic research and scientific papers

Synthesis of Functionalized α-Vinyl Aldehydes from Enaminones

An efficient RhII-catalyzed synthesis of functionalized α-vinyl aldehydes with high E/Z stereoselectivity was developed. The reaction mediates the cyclopropanation of enaminones with vinyl carbenoids that are generated from cyclopropenes in situ to give the aminocyclopropane intermediates. Selective C?C bond cleavage of the cyclopropane intermediates leads to formation of α-vinyl aldehyde derivatives with high E/Z selectivity. This method proceeds at room temperature under very mild reaction conditions and works with a broad substrate scope.

Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes

A highly stereocontrolled syn-addition of silicon nucleophiles across cyclopropenes with two different geminal substituents at C3 is reported. Diastereomeric ratios are excellent throughout (d.r.≥98:2) and enantiomeric excesses usually higher than 90 %, even reaching 99 %. This copper-catalyzed C?Si bond formation closes the gap of the direct synthesis of α-chiral cyclopropylsilanes.

Tandem Hydroalumination/Cu-Catalyzed Asymmetric Vinyl Metalation as a New Access to Enantioenriched Vinylcyclopropane Derivatives

Herein, we report the first enantio- and diastereoselective addition of stereodefined vinyl organometallic reagents to cyclopropenes. The operationally simple tandem hydroalumination and copper-catalyzed vinylmetalation allows for the unique access of a diverse set of enantioenriched vinylcyclopropane derivatives.

Asymmetric Nitrone Synthesis via Ligand-Enabled Copper-Catalyzed Cope-Type Hydroamination of Cyclopropene with Oxime

We report realization of the first enantioselective Cope-type hydroamination of oximes for asymmetric nitrone synthesis. The ligand promoted asymmetric cyclopropene "hydronitronylation" process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C-N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis.

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.

Improved preparative route toward 3-arylcyclopropenes

A convenient preparative protocol for the synthesis of various 3-arylcyclopropenes in a multigram scale is disclosed. Optimization of the reaction conditions and isolation procedures allowed for significant improvement of the chemical yields of these strained products. The described protocol was used for efficient preparation of a series of 3-methyl-3-arylcyclopropenes possessing different substituents in the aromatic ring. The effect of substitution in the aryl group on the stability of 3-arylcyclopropenes, as well as the corresponding precursors, is discussed.

SELECTIVITY IN THE REACTIONS OF 3,3-DISUBSTITUTED CYCLOPROPENES WITH NITRILE OXIDES

The reactions of 3-R-3-R'-disubstituted cyclopropenes with nitrile oxides lead to the formation of 4,6,6-trisubstituted 2-oxa-3-azabicyclohex-3-enes, which can be isolated with high yields.Substituents at C3 of the cyclopropane ring (phe