3709-32-8

Upstream product

• 100-52-7 benzaldehyde 
• 2033-24-1 cycl-isopropylidene malonate 
• 1214-54-6 5-benzylidene Meldrum's acid 
• 1774-47-6 trimethylsulfoxonium iodide 
• 100-42-5 styrene 
• 34107-52-3 2,2-dimethyl-5-(phenyl-λ³-iodaneylidene)-1,3-dioxane-4,6-dione 
• 70775-39-2 dimethylsulfoxonium methylide 
• 186581-53-3 diazomethane 

Downstream Products

• 97364-70-0 Methyl 1-methoxycarbonylamino-2-phenyl-cyclopropanecarboxylate (E) 
• 97364-56-2 (1S,2R)-1-Methoxycarbonylamino-2-phenyl-cyclopropanecarboxylic acid 
• 3200-81-5 (E)-1-amino-2-phenylcyclopropanecarboxylic acid hydrochloride 
• 14224-51-2 1,1-Bis-(hydroxymethyl)-2-phenyl-cyclopropan 
• 97364-76-6 1-methoxycarbonyl-2-phenylcyclopropanecarboxylic acid 
• 97364-47-1 (1R,2R)-1-Carbamoyl-2-phenyl-cyclopropanecarboxylic acid 
• 3709-34-0 2-phenyl-1,1-cyclopropanedicarboxylic acid 
• 3709-35-1 1,1-bis(methoxycarbonyl)-3-methoxy-3-phenylpropane 
• 3709-20-4 dimethyl 2-phenyl-1,1-cyclopropanedicarboxylate 

Relevant academic research and scientific papers

Asymmetric Cyclopropanation of Olefins with an in situ Generated Phenyliodonium Ylide

A procedure for the in situ generation of the phenyliodonium ylide (2) derived from Meldrum's acid (1) and its Rh(II)-catalyzed decomposition to afford an intermediate metallocarbene is described. In the presence of olefins, cyclopropanes are formed with yields and enantioselectivity comparable to that resulting from cyclopropanation with the isolated ylide 2.

Protic Ionic Liquid as Reagent, Catalyst, and Solvent: 1-Methylimidazolium Thiocyanate

We propose a new concept of the triple role of protic ionic liquids with nucleophilic anions: a) a regenerable solvent, b) a Br?nsted acid inducing diverse transformations via general acid catalysis, and c) a source of a nucleophile. The efficiency of this strategy was demonstrated using thiocyanate-based protic ionic liquids for the ring-opening of donor-acceptor cyclopropanes. A wide variety of activated cyclopropanes were found to react with 1-methylimidazolium thiocyanate under mild metal-free conditions via unusual nitrogen attack of the ambident thiocyanate ion on the electrophilic center of the three-membered ring affording pyrrolidine-2-thiones bearing donor and acceptor substituents at the C(5) and C(3) atoms, respectively, in a single time-efficient step. The ability of 1-methylimidazolium thiocyanate to serve as a triplex reagent was exemplarily illustrated by (4+2)-annulation with 1-acyl-2-(2-hydroxyphenyl)cyclopropane, epoxide ring-opening and other organic transformations.

Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes

The kinetics of the ring-opening reactions of thiophenolates with geminal bis(acceptor)-substituted cyclopropanes in DMSO at 20 °C was monitored by photometric methods. The determined second-order rate constants of the SN2 reactions followed linear relationships with Mayr nucleophilicity parameters (N/sN) and Br?nsted basicities (pKaH) of the thiophenolates as well as with Hammett substituent parameters (σ) for groups attached to the thiophenolates. Phenyl-substituted cyclopropanes reacted by up to a factor of 15 faster than their unsubstituted analogues, in accord with the known activating effect of adjacent π-systems in SN2 reactions. Variation of the electronic properties of substituents at the phenyl groups of the cyclopropanes gave rise to parabolic Hammett relationships. Thus, the inherent SN2 reactivity of electrophilic cyclopropanes is activated by electron-rich π-systems because of the more advanced C1?C2 bond polarization in the transition state. On the other hand, electron-poor π-systems also lower the energetic barriers for the attack of anionic nucleophiles owing to attractive electrostatic interactions.

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal-free Cyclopropanation with Alkenes

A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures of alkenes and β-dicarbonyl-derived iodonium ylides are irradiated with light from blue LEDs. This metal-free synthesis gives cyclopropanes in yields

N-Iodosuccinimide-Initiated Spirocyclopropanation of Styrenes with 1,3-Dicarbonyl Compound for the Synthesis of Spirocyclopropanes

Herein is reported an N-iodosuccinimide-initiated spirocyclopropanation reaction of styrenes with 1,3-dicarbonyl compounds in the presence of white LED light. The reaction proceeds via two C-H and two C-I bond cleavage event, along with two C-C bond forma

Fused dihydrofurans from the one-pot, three-component reaction of 1,3-cyclohexanedione, iodobenzene diacetate and alkenes

The one-pot, three-component reactions of substituted 1,3- cyclohexanediones, iodobenzene diacetate and alkenes, under photochemical activation, yields fused dihydrofuran derivatives in good yield via the in situ formation of iodonium ylides.

GaCl3-catalyzed insertion of diazene derivatives into the cyclopropane ring

(Chemical Equation Presented) GaCl3 has been found to efficiently catalyze the formal cycloadditions of diazene derivatives 6 onto 2-arylcyclopropane-1,1-dicarboxylates 5, giving rise to the pyrazolidine derivatives 7. The insertion into the cy

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.

Rhodium(II)-catalyzed olefin cyclopropanation with the phenyliodonium ylide derived from Meldrum's acid

The phenyliodonium ylide 3a derived from Meldrum's acid reacts with olefins in the presence of Rh(II) carboxylate catalysts to afford cyclopropanes. The reaction is stereospecific. Enantioselectivities of up to 63% have been observed for the cyclopropanation of pent-1-ene. No 1,3-cycloadducts are formed between 3a and polarized olefins such as furan or 2,3-dihydrofuran.

SYNTHESIS OF E AND Z 1-AMINO-2-ARYL(ALKYL)-CYCLOPROPANECARBOXYLIC ACID via MELDRUM DERIVATIVES

The reaction of 5-arylidene(alkylidene)-2,2-dimethyl-1,3-dioxane-4,6-diones (1) (Meldrum's acid derivatives) with dimethylsulfoxonium methylide gave 1-aryl(alkyl)-6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro octanes (2) which , on treatment with sodium meth