17413-48-8

Upstream product

• 6526-76-7 (S)-(+)-1-bromo-1-methyl-2,2-diphenylcyclopropane 
• 93713-82-7 (+/-)-1,3-dimethoxy-1,1-diphenylbutane 
• 530-48-3 1,1-Diphenylethylene 
• 50324-00-0 <2,2-Diphenyl-cyclopropyl-(1)>-methyl-p-toluolsulfonat 
• 187737-37-7 propene 
• 908093-98-1 diazodiphenylmethane 
• 495-45-4 dypnone 
• 74-85-1 ethene 
• 26929-50-0 4-Methoxy-4,4-diphenyl-but-1-en 
• 32812-52-5 1-bromo-2,2-diphenyl cyclopropane 
• 77-78-1 dimethyl sulfate 
• 37555-48-9 2,2-diphenylcyclopropylmethanol 
• 93-55-0 1-phenyl-propan-1-one 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 6393-07-3 1,2,2-Triphenyl-pentan 
• 93632-70-3 2-methoxy-4,4-diphenylbutane 

Relevant academic research and scientific papers

Bromomethyl Silicate: A Robust Methylene Transfer Reagent for Radical-Polar Crossover Cyclopropanation of Alkenes

A general protocol for visible-light-induced cyclopropanation of alkenes was developed with bromomethyl silicate as a methylene transfer reagent, offering a robust tool for accessing highly valuable cyclopropanes. In addition to α-aryl or methyl-substituted Michael acceptors and styrene derivatives, the unactivated 1,1-dialkyl ethylenes were also shown to be viable substrates. Apart from realizing the cyclopropanation of terminal alkenes, the methyl transfer reaction has been further demonstrated to be amenable to the internal olefins. The photocatalytic cyclopropanation of 1,3-bis(1-arylethenyl)benzenes was also achieved, giving polycyclopropane derivatives in excellent yields. With late-stage cyclopropanation as the key strategy, the synthetic utility of this transformation was also demonstrated by the total synthesis of LG100268.

Redox-Neutral Photocatalytic Cyclopropanation via Radical/Polar Crossover

A benchtop stable, bifunctional reagent for the redox-neutral cyclopropanation of olefins has been developed. Triethylammonium bis(catecholato)iodomethylsilicate can be readily prepared on multigram scale. Using this reagent in combination with an organic photocatalyst and visible light, cyclopropanation of an array of olefins, including trifluoromethyl- and pinacolatoboryl-substituted alkenes, can be accomplished in a matter of hours. The reaction is highly tolerant of traditionally reactive functional groups (carboxylic acids, basic heterocycles, alkyl halides, etc.) and permits the chemoselective cyclopropanation of polyolefinated compounds. Mechanistic interrogation revealed that the reaction proceeds via a rapid anionic 3-exo-tet ring closure, a pathway consistent with experimental and computational data.

Polylithiumorganic compounds. Part 29: C,C Bond cleavage of phenyl substituted and strained carbocycles using lithium metal

The reaction of phenyl substituted cyclopropanes phenylcyclopropane and 1,1-diphenylcyclopropane, phenyl substituted bicyclobutanes 1- phenylbicyclobutane, 1-methyl-3-phenylbicyclobutane, 1-methyl-2,2- diphenylbicyclobutane, as well as phenyl substituted spiropentanes phenylspiropentane and 1,1-diphenylspiropentane with lithium metal or lithium di-t-butylbiphenyl (LiDBB) was investigated. Under suitable reaction conditions and choice of solvent in all cases cleavage of the single bond next to the activating phenyl group was observed. The dilithiumorganic compounds thus obtained are sufficiently stable and can be trapped with electrophiles. Lithium hydride elimination is observed as follow-up reaction only in a few cases. The corresponding anions of the strained ring systems 1-lithio-2,2- diphenylcyclopropane, 1-lithio-3-phenylbicyclobutane, 1-lithio-3-methyl-2,2- diphenylbicyclobutane, and 1-lithio-4-phenylspiropentane, which can be obtained by lithium bromine exchange or by metalation of the unsubstituted carbocycle, do not show any cleavage upon reaction with lithium metal. The reaction of phenyl substituted cyclopropanes, bicyclobutanes as well as spiropentanes with lithium metal with formation of highly reactive dilithiumorganic compounds was investigated. In all cases cleavage of the bond next to the phenyl substituent(s) was observed.

Access to functionalized cyclopropylcarbinyl compounds from homoallylic ethers via zirconocene intermediates

Cyclopropylcarbinylzirconium complexes were generated from homoallylic ethers and zirconocene (Cp2ZrCl2/2n-BuLi). They underwent further in situ transformations that is, bromination-substitution, transmetallation-functionalization and insertion reactions to afford various cyclopropylcarbinyl derivatives. In contrast, ring-opening products could be selectively obtained by treating the zirconium complex with MeLi, prior to functionalization.

Zirconium-mediated conversion of homoallylic ethers into cyclopropane derivatives

Homoallylic ethers react with Cp2ZrCl2/2 n-BuLi reagent to afford cyclopropane derivatives. Cyclopropylcarbinyl-homoallyl rearrangements involving zirconium species are observed depending on the substrate structure.

Cationic and neutral diphenyldiazomethanerhodium(I) complexes as catalytically active species in the C-C coupling reaction of olefins and diphenyldiazomethane

Cationic rhodium(I) complexes cis-[Rh(acetone)2(L)(L')]+ (2: L=L'=C8H14; 3: L=C8H14; L'=PiPr3; 4: L= L'=PiPr3), prepared from [{RhCl-(C8H14)

Picosecond radical kinetics. Ring openings of phenyl substituted cyclopropylcarbinyl radicals

Rate constants for ring openings of the trans-(2-phenylcyclopropyl)carbinyl radical (1a), the cis-(2-phenylcyclopropyl)carbinyl radical (1b), and the (2,2-diphenylcyclopropyl)carbinyl radical (1c) were studied by competition kinetics using PTOC esters as radical precursors and hydrogen atom transfer trapping from benzeneselenol as the basis reaction. Radical la was studied in two solvents, toluene and THF; the experimental Arrhenius function for ring opening of 1a was log (kr·s) = 13.9 - 33/2.3RT (R in kcal/mol). It is possible that the immediate precursor to 1a, acyloxy radical 3a, suffers a concomitant decarboxylation-ring opening process that competes with simple decarboxylation leading to 1a. The experimental rate constant for ring opening of la at 25°C is 3 × 1011 s-1. Preliminary kinetic studies of radicals 1b and 1c gave Arrhenius functions of log (kr·s) = 13.9 - 3.1/2.3RT and log (kr·s) = 13.1 - 2.0/2.3RT, respectively, and the respective rate constants for ring openings at 25°C are 4 and 5 × 1011 s-1. Rate constants for ring openings of substituted cyclopropylcarbinyl radicals were estimated by Marcus theory using the known rate constants and equilibrium constant for the parent system and expected ΔG° values for the substituted systems. From these results, the estimated rate constants at 25°C for ring opening of 1a and 1b were 1 × 1011 s-1 and that for le was 4 × 1011 s-1. Precursors to radicals 1, such as the corresponding hydrocarbons, represent hypersensitive radical probes that, in principle, can provide unequivocal conclusions regarding the intermediacy of a radical in a reaction.

Reaction of Chiral Cyclopropyl Halides with SmI2

Reductions of (S)-(+)-1-bromo-1-methyl-2,2-diphenylcyclopropane (7), (S)-(+)-1-bromo-1-(methoxymethyl)-2,2-diphenylcyclopropane (19), and (R)-(-)-1-fluoro-1-iodo-2,2-diphenylcyclopropane (11) with samarium(II) iodide is reported.Evidence for a samarium(III) intermediate in the reaction is presented.

DIRECT CONVERSION OF ALKENES INTO METHYL-SUBSTITUTED CYCLOPROPANES USING AN ORGANOIRON ETHYLIDENE TRANSFER REAGENT

(η5-C5H5)(CO)2FeCH(CH3)SPh (8) serves as a quite useful reagent for the transfer of ethylidene groups to alkenes to give methyl-substituted cyclopropanes in good yields.The reaction is accomplished by allowing 8 to react with an alkylating agent such as trimethyloxonium tetrafluoroborate or methyl fluorosulfonate in the presence of the alkene substrate.The active ethylidene transfer reagent is apparently a sulfonium salt which is too reactive to be isolated under normal conditions.In all csases, cyclopropanes are obtained stereospecifically with respect to the configuration of the starting alkenes, and with certain classes of substrates such as cis-disubstituted alkenes, the reaction also occurs with very high syn-stereoselectivity.