80246-72-6

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 109-66-0 pentane 

Downstream Products

• 66225-51-2 3-ethyl-1-pentanol 

Relevant academic research and scientific papers

Alkoxydiaminophosphine Ligands as Surrogates of NHCs in Copper Catalysis

A family of phosphine ligands containing a five-membered ring similar to the popular N-heterocyclic carbene ligands and an alkoxy third substituent has been developed. These alkoxydiaminophosphine ligands (ADAP) can be generated in one pot and reacted with a copper(I) source leading to the high yield isolation of complexes [(ADAP)CuX]2 (X=Cl, Br). The dinuclear nature of these compounds has been established by means of X-ray studies and DOSY experiments. A screening of the catalytic properties of these complexes toward carbene-transfer reactions from diazocompounds to C?H bonds (alkane, arene), olefins or N?H bonds, as well as in CuAAC or nitrene transfer reactions have shown a performance at least similar, if not better, than their (NHC)CuCl analogues, opening a new window in copper catalysis with these readily tunable ADAP ligands.

Water as the Reaction Medium for Intermolecular C-H Alkane Functionalization in Micellar Catalysis

A series of alkanes CnH2n+2 have been functionalized in water as the reaction medium, using a silver-based catalyst, upon the insertion of carbene (CHCO2Et from N2CHCO2Et) groups into the carbon-hydrogen bonds of hexane, cyclohexane, or 2-methylbutane, among others. The regioselectivity toward the distinct reaction sites is identical to that found in neat alkane, the water-based system allowing the use of a much shorter excess of the hydrocarbon. This is the first example of the intermolecular functionalization of alkanes with this strategy in water. The functionalized alkanes partially undergo the incorporation of a second carbene unit to provide α-(acyloxy)acetates, in an unprecedented tandem reaction of this nature.

Functionalization of CnH2n+2 Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds

The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attributed to the effect of the carbon dioxide molecules that withdraw electron density from the fluorine atoms of the ligand, which enhances the electrophilic nature of the metal center. DFT studies validated this proposal.

Catalytic functionalization of methane and light alkanes in supercritical carbon dioxide

The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10-3 s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, propane, butane, and isobutane.

Silver-catalyzed C-C bond formation between methane and ethyl diazoacetate in supercritical CO2

Even in the context of hydrocarbons' general resistance to selective functionalization, methane's volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH4) with ethyl diazoacetate (N2CHCO2Et) to yield ethyl propionate (CH3CH2CO2Et). The use of supercritical carbon dioxide (scCO2) as the solvent is key to the reaction's success. Although the catalyst is only sparingly soluble in CH4/CO2 mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.

Intermetallic coinage metal-catalyzed functionalization of alkanes with ethyl diazoacetate: Gold as a ligand

The complexes [Au2M2(C6F5) 4(NCMe)2]n (M = Cu, 1; M = Ag, 2) have been tested as catalysts for the functionalization of alkanes by the carbene insertion methodology, using ethyl diazoacetate as the carbene source. Moderate to high conversions have been obtained. The observed selectivities seem to favor the proposal that the active metal for catalysis is the Cu/Ag center, the Au(C6F5)2 unit acting as a spectator ligand in both cases.