57941-73-8Relevant articles and documents
Carbene Transfer and Carbene Insertion Reactions Catalyzed by a Mixed-Ligand Copper(I) Complex
Brenna, Stefano,Ardizzoia, G. Attilio
, p. 3336 - 3342 (2018/07/13)
The catalytic activity of the mixed-ligand copper(I) complex [Cu(PPh3)2(κ2-O,O"-lact)] (1) {lact = l-(+)-lactate} has been investigated in carbene transfer and carbene insertion reactions. Complex 1 catalytically promoted the diastereoselective cyclopropanation of olefins in the presence of ethyl diazoacetate (EDA), under mild conditions, and with a low catalyst loading (1 mol-%). In the case of internal alkenes, a trans/cis ratio of up to 93:7 was reached. Moreover, compound 1 easily promoted the insertion of the carbene fragment deriving from the decomposition of ethyl diazoacetate into O–H (alcohols and phenols) and N–H (amine) bonds, with formation of the corresponding ethyl 2-alkoxyacetate, ethyl 2-phenoxyacetate, and ethyl 2-aminoacetate derivatives in good to high yields.
InCl3 catalyzed carbene insertion into O-H bonds: Efficient synthesis of ethers
Radha Krishna, Palakodety,Prapurna, Y. Lakshmi,Alivelu, Munagala
experimental part, p. 3460 - 3462 (2011/06/27)
An efficient InCl3 mediated insertion of the carbene fragment (:CHCO2Et), generated in situ from ethyl diazoacetate into O-H bond of a series of saturated and unsaturated alcohols under mild conditions has been developed to afford the corresponding ethers as exclusive products in good to high yields (70-95%) and in shorter reaction times. In the case of unsaturated alcohols, the reaction proceeded with unprecedented selectivity resulting in ethers as the only products and in high yields.
Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides
Zhu, Zuolin,Espenson, James H.
, p. 9901 - 9907 (2007/10/03)
Methylrhenium trioxide (CH3ReO3 or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, α-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of α-phenoxy ethyl acetates. The use of EDA to form α-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and tobenzil; at the same time the epoxide was converted to an olefin. These results provide further support for the proposed intermediate, a cyclic species containing Re, O, and CHCO2Et (or, occasionally, CPhC(O)Ph)in a three-membered ring.
