127604-92-6

Usage

Common Use

Building block in the synthesis of various pharmaceuticals and agrochemicals

Chirality

Chiral compound with the (R)-enantiomer being more prevalent

Cyclopropane ring

A three-membered carbon ring

Chlorophenyl group

A phenyl group with a chlorine atom substitution

Ester Functionality

Dimethyl ester form

Solubility

More readily soluble in organic solvents due to the dimethyl ester form

Versatility

Used in the production of drugs and other organic compounds due to its versatile chemical structure and reactivity

Upstream product

• 1073-67-2 4-vinylbenzyl chloride 
• 6773-29-1 dimethyl diazomalonate 
• 108-59-8 malonic acid dimethyl ester 
• 1379474-24-4 dimethyl 2-((2-methoxyphenyl)-λ³-iodanylidene)malonate 
• 204581-98-6 (R)-4-(4-Chloro-phenyl)-[1,3,2]dioxathiolane 2-oxide 
• 127604-92-6 dimethyl 2-(4-chlorophenyl)cyclopropane-1,1-dicarboxylate 
• 3376-23-6 C-phenyl-N-methylnitrone 
• 127604-90-4 (1R,7S,10R)-1-(4-Chloro-phenyl)-7-isopropyl-10-methyl-5,12-dioxa-dispiro[2.2.5.2]tridecane-4,13-dione 
• 130143-05-4 (7S,10R)-3-(4-Chloro-benzylidene)-7-isopropyl-10-methyl-1,5-dioxa-spiro[5.5]undecane-2,4-dione 
• 186581-53-3 diazomethane 
• 52927-44-3 dimethyl 2-(4-chlorobenzylidene)malonate 
• 868-26-8 dimethyl 2-bromomalonate 
• 104-88-1 4-chlorobenzaldehyde 
• 1774-47-6 trimethylsulfoxonium iodide 

Downstream Products

• 851293-07-7 dimethyl (2S)-2-(4-chlorophenyl)cyclopropane-1,1-dicarboxylate 
• 1191241-07-2 dimethyl 2-(2-(4-chlorophenyl)-4-oxo-4-phenylbutyl)malonate 
• 1315456-00-8 C₂₀H₁₈ClNO₄ 
• 1361945-31-4 methyl 5-(4-chlorophenyl)-8-oxo-3,4,5,6,7,8-hexahydro-2H-chromene-7-carboxylate 
• 1361945-34-7 5-(4-chlorophenyl)-3,4,6,7-tetrahydro-2H-chromen-8(5H)-one 
• 1402823-81-7 (Z)-dimethyl 2-(allylimino)-5-(4-chlorophenyl)dihydrothiophene-3,3(2H)-dicarboxylate 
• 1402824-02-5 dimethyl 1-benzyl-2-oxo-5-(4-chlorophenyl)pyrrolidine-3,3-dicarboxylate 
• 1402823-95-3 (E)-dimethyl 5-(4-chlorophenyl)-1-isopropyl-2-(isopropylimino)pyrrolidine-3,3-dicarboxylate 

Relevant academic research and scientific papers

Rh(II)-catalyzed enantioselective cyclopropanation of olefins with dimethyl malonate via in situ generated phenyliodonium ylide

(Chemical Equation Presented) Olefins are cyclopropanated with dimethyl malonate (1a) iodosylbenzene (Phl=O) and a Rh(II) carboxylate catalyst via an in situ generated phenyliodonium ylide (1c). Enantioselectivities of up to 90% for 4-bromostyrene and 98% for pent-1-ene have been observed with (S)-N-4-bromo-1,8-naphthanoyl-tert-leucine (4c) as the chiral ligand. The same catalyst was effective for olefin cyclopropanation with Meldrum's acid, giving cyclopropanes with 96% (with styrene) and 87% ee (with pent-1-ene), respectively.

Diazo compounds and phenyliodonium ylides in inter- and intramolecular cyclopropanations catalyzed by dirhodium(II). Synthesis and chiral resolution by GC versus HPLC

The dirhodium(II)-catalyzed intermolecular cyclopropanation of a set of olefins with either diazo free phenyliodonium ylides or diazo compounds afforded cyclopropanes derived from Meldrum's acid, dimethyl malonate, (silanoxyvinyl)diazoacetates, 3,3,3-trifluoro-2-diazopropionate, ethyl diazo(triethyl)- and (dimethylphenyl)silylacetate with moderate to high yield in either racemic or enantio-enriched forms. The intramolecular cyclopropanation of triethylsilyl-substituted allyl diazo-acetates in the presence of the chiral rhodium(II) catalyst [Rh2(s-nttl)4] in toluene afforded the corresponding cyclopropanes with up to 37% ee. An efficient chiral separation method based on enantioselective GC and HPLC was developed. The method provides information about the chemical yields of the cyclopropane products, enantioselectivity, substrate specifity, and catalytic activity of the chiral catalysts used in the inter- and intramolecular cyclopropanation reactions and avoids time-consuming work-up procedures. Springer-Verlag 2005.

Highly enantioselective and diastereoselective cycloaddition of cyclopropanes with nitrones and its application in the kinetic resolution of 2-substituted cyclopropane-1,1-dicarboxylates

(Chemical Equation Presented) The multitalented catalyst 1/Ni(ClO 4)2 mediates both title processes (see scheme). Together the efficient asymmetric cycloaddition and a kinetic resolution/ cycloaddition provide access to both enantiom

A route to highly functionalized-enaminoesters via a domino ring-opening cyclization/decarboxylative tautomerization sequence of donor-acceptor cyclopropanes with substituted malononitriles

An unprecedented and domino synthetic strategy for the synthesis of highly functionalized carbocyclic-enaminoesters bearing an all-carbon quaternary center via Yb(OTf)3-catalyzed ring-opening cyclization/decarboxylative tautomerization of donor-acceptor cyclopropanes with 2-alkyl malononitriles in excellent yields is described. The products are obtained as a single diastereomer in most cases where the nitrile and aryl groups are aligning in a cis orientation across the ring.

(3+2)-Cycloaddition of Donor-Acceptor Cyclopropanes with Thiocyanate: A Facile and Efficient Synthesis of 2-Amino-4,5-dihydrothiophenes

An easy and efficient route to obtain 2-amino-4,5-dihydrothiophenes is presented. A formal (3+2)-cycloaddition of donor-acceptor cyclopropanes and ammonium thiocyanate catalyzed by Yb(OTf) 3delivers the desired products in good to excellent yields. A broad range of functional groups is tolerated during this process.

(3 + 2)-Cycloaddition of Donor-Acceptor Cyclopropanes with Selenocyanate: Synthesis of Dihydroselenophenes and Selenophenes

We present a Lewis-acid-catalyzed (3 + 2)-cycloaddition of donor-acceptor cyclopropanes and selenocyanate (as its tetramethylammonium salt) for the synthesis of dihydroselenophenes. The transformation proceeded with moderate to excellent yields and showed a high functional group tolerance. Further oxidation using DDQ delivered selenophenes.

Stereospecific copper(II)-catalyzed tandem ring opening/oxidative alkylation of donor-acceptor cyclopropanes with hydrazones: Synthesis of tetrahydropyridazines

Aerobic copper(II)-catalyzed tandem ring opening and oxidative C-H alkylation of donor-acceptor cyclopropanes with bisaryl hydrazones is accomplished to produce tetrahydropyridazines, in which copper(II) plays dual role as a Lewis acid as well as redox catalyst. The reaction is stereospecific, and optically active cyclopropanes can be reacted with high optical purities (89-98% enantiomeric excess). The substrate scope, functional group tolerance, dual role of the copper(II) catalyst, and the use of air as an oxidant are the important practical features. A product bearing a 3-bromoaryl group can be subjected to Pd-catalyzed Suzuki coupling with boronic acid in high yield.

Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Br?nsted Acid in Hexafluoroisopropanol

A general, Br?nsted acid catalyzed method for the room temperature, nucleophilic ring opening of donor-acceptor cyclopropanes in fluorinated alcohol solvent, HFIP, is described. Salient features of this method include an expanded cyclopropane scope, including those bearing single keto-acceptor groups and those bearing electron-deficient aryl groups. Notably, the catalytic system proved amenable to a wide range of nucleophiles including arenes, indoles, azides, diketones, and alcohols.

An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters

A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.

Formal Insertion of Thioketenes into Donor-Acceptor Cyclopropanes by Lewis Acid Catalysis

Donor-acceptor cyclopropanes were reacted under Lewis acid catalysis with 3-thioxocyclobutanones as surrogates for disubstituted thioketenes. A broad scope of 2-substituted tetrahydrothiophenes with a semicyclic double bond was obtained under mild conditions with high functional group tolerance and in excellent yield. A sequence of a formal [3 + 2]-cycloaddition followed by the subsequent release of disubstituted ketene is postulated as the mechanism.