40474-22-4

Upstream product

• 13735-81-4 1-styrenyloxytrimethylsilane 
• 98-83-9 isopropenylbenzene 
• 6832-16-2 methyl diazoacetate 
• 22293-10-3 (1-diazoethyl)benzene 
• 292638-85-8 acrylic acid methyl ester 

Downstream Products

• 114326-42-0 methyl cis-1-(hydroxydiphenylmethyl)-2-methyl-2-phenylcyclopropanecarboxylate 
• 54541-41-2 methyl 2-methyl-3-phenylbutanoate 
• 20881-29-2 dihydro-α-norcurcumenic acid methylester 
• 25080-84-6 3-Methyl-3-phenylbutansaeure-methylester 

Relevant academic research and scientific papers

Dinuclear ruthenium(I) complexes of the type [Ru2(CO) 4L2] with carboxylate or 2-pyridonate ligands: Evaluation as catalysts for olefin cyclopropanation with diazoacetates

Dinuclear ruthenium(I,I) carboxylate complexes [Ru2(CO) 4(μ-OOCR)2]n (R = CH3 (1a), C3H7 (1b), H (1c), CF3 (1d)) and 2-pyridonate complex [Ru2(CO)4(μ-2-pyridonate)2] n (3) catalyze efficiently the cyclopropanation of alkenes with methyl diazoacetate. High yields are obtained with terminal nucleophilic alkenes (styrene, ethyl vinyl ether, α-methylstyrene), medium yields with 1-hexene, cyclohexene, 4,5-dihydrofuran and 2-methyl-2-butene. The E-selectivity of the cyclopropanes obtained from the monosubstituted alkenes and the cycloalkenes decreases in the order 1b > 1a > 1d > 1c. The cyclopropanation of 2-methyl-2-butene is highly syn-selective. Several complexes of the type [Ru2(CO)4(μ-L1) 2]2 (4) and (5), [Ru2(CO)4(μ- L1)2L2] (L2 = CH3OH, PPh3) (6)-(9) and [Ru2(CO)4(CH 3CN)2(μ-L1)2] (10) and (11), where L1 is a 6-chloro- or 6-bromo-2-pyridonate ligand, are also efficient catalysts. Compared with catalyst 3, a halogen substituent at the pyridonate ligand affects the diastereoselectivity of cyclopropanation only slightly.

Dirhodium(II) tetrakis(perfluoroalkylbenzoates) as partially recyclable catalysts for carbene transfer reactions with diazoacetates

Three highly fluorinated dirhodium(II) tetrakis(benzoates), [Rh2(O2CRF)4, RF=C6H4-4-C6F13 (3) and C6H3-3,5-di(CnF2n+1) (n=6: 4; n=8: 5)], have been prepared and characterized. Only 4 and 5 are suited for applications in fluorous synthesis due to their excellent solubility in fluorous solvents. They were found to catalyze the following carbenoid reactions of diazo compounds in the fluorous solvents 1,1,2-trichloro-1,2,2-trifluoroethane and perfluoro(methylcyclohexane): cyclopropanation of styrenes using methyl diazoacetate, intermolecular carbene C-H insertion into hexane with methyl diazoacetate, and intramolecular aromatic C-H insertion of an α-diazo-β-ketoester. Except for the second reaction type, the catalyst could be recovered to a high extent by a liquid-liquid extraction (fluorous solvent - dichloromethane) due to its preference for the fluorous solvent. For the cyclopropanation reactions, the recovered catalyst was used in four subsequent reaction/workup cycles without significant loss of activity. In contrast, the catalyst could not be recovered from the carbenoid C-H insertion reaction with hexane; apparently, some by-products of this sluggish reaction, such as carbene dimers and oligomers, caused the deactivation or destruction of the catalyst.

A fluorous phase approach to rhodium-catalyzed carbenoid reactions with diazoacetates

The cyclopropanation of alkenes with methyl diazoacetate in dichloromethane was catalyzed by rhodium(II) carboxylates containing a perfluoralkyl chain (Rh2L4, L = OOCC7F15 and OOC-C6H4-4-C

Polymeric dicarbonyl ruthenium(I) acetate - An efficient catalyst for alkene cyclopropanation with diazoacetates

The polymeric complex [Ru2(CO)4(μ-OAc)2](n) is the first Ru(I) catalyst that efficiently catalyzes cyclopropanation of alkenes with diazoacetic esters. The related dinuclear catalyst Ru2(CO)4(μ-OAc)2(MeCN)2 shows a similar performance only for cyclopropanation of monosubstituted alkenes.

Synthesis of 2-Siloxy-substituted Methyl Cyclopropanecarboxylates

2-Siloxy-substituted methyl cyclopropanecarboxylates C - useful building blocks in synthesis - are obtained in great variety and with good yields from the silyl enol ethers E and methyl diazoacetate (D) under copper salt catalysis.Whereas the regiochemical and stereochemical properties of E are completely transferred to the cyclopropanes C, the stereoselectivity concerning the position of the methoxycarbonyl group is low.The 1H and 13C data used to determine the configurations of compounds C are discussed.

Deprotonation and Diastereoselective Alkylation of Methyl Cyclopropanecarboxylates

Using model compounds it is demonstrated when deprotonation of methyl cyclopropanecarboxylates leads to ester condensation products and when alkylation of the ester enolate can be performed.Under certain structural conditions (steric and electronic effect