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Synthesis of Diazo Compounds


Recent Literature

The Pd-catalyzed reaction between aryl or vinyl iodides and ethyl diazoacetate (EDA) provides cross-coupling products in good yields.
C. Peng, J. Cheng, J. Wang, J. Am. Chem. Soc., 2007, 129, 8708-8709.

C. Peng, J. Cheng, J. Wang, J. Am. Chem. Soc., 2007, 129, 8708-8709.

C. Peng, J. Cheng, J. Wang, J. Am. Chem. Soc., 2007, 129, 8708-8709.

A safe and fast method for the production of β-hydroxy-α-diazoesters involves the formation of ethyl diazoacetate in situ and the addition to several aldehydes in a two-step continuous flow microreactor setup. In a three-step sequence, Rhodium acetate catalyzes a subsequent 1,2-hydride shift to give access to β-keto esters.
S. T. R. Müller, D. Smith, P. Hellier, T. Wirth, Synlett, 2014, 25, 871-875

Silica-supported tetramethylguanidine catalyst was prepared and effectively used in the aldol-type coupling of aldehydes with ethyl diazoacetate to afford the corresponding α-diazo-β-hydroxy esters in very good yields. The catalyst can be reused for a number of cycles with almost consistent activity by a simple filtration.
P. R. Likhar, S. Roy, M. Roy, M. S. Subhas, M. Lakshmi Kantam, Synlett, 2008, 1283-1286.

A transition-metal-free direct carboxylation of the ipso-C(sp2)-H bond of diazo compounds proceeds at ambient temperature under atmospheric pressure of carbon dioxide in the presence of a weak base. A series of unsymmetrical 1,3-diester/keto/amide diazo compounds are obtained with good yields and good functional group compatibility.
Q. Liu, M. Li, R. Xiong, F. Mo, Org. Lett., 2017, 19, 6756-6759.

The reaction of diazo(trimethylsilyl)methylmagnesium bromide with aldehydes or ketones gave 2-diazo-2-(trimethylsilyl)ethanols, which were applied to the synthesis of di- and trisubstituted pyrazoles via [3+2] cycloaddition reaction with ethyl propiolate or dimethyl acetylenedicarboxylate.
Y. Hari, S. Tsuchida, R. Sone, T. Aoyama, Synthesis, 2007, 3371-3375.

An axially chiral dicarboxylic acid has been applied to a highly enantioselective Mannich reaction of arylaldehyde N-Boc imines and diazo compounds as a new class of chiral hydrogen-bonding catalyst.
T. Hashimoto, K. Maruoka, J. Am. Chem. Soc., 2007, 129, 10054-10055.

N-Tosyl diazoketamines were prepared by addition of the ethyl α-diazoacetate anion to N-sulfonylimines. A subsequent diazo decomposition of the diazoketamines with Rh2(OAc)4 as catalyst provided α-aryl-β-enamino esters in good yields and high stereoselectivity via aryl migration.
N. Jiang, Z. Qu, J. Wang, Org. Lett., 2001, 3, 2989-2992.

An improved Arndt-Eistert synthesis to obtain α-diazoketones allows the efficient transformation of acid halides using a stoichiometric amount of diazomethane in the presence of calcium oxide, without concomitant ketene or haloketone formation. The obtained α'-brominated-α-diazoketones were employed for the synthesis of interesting α-arylamino-α′-halomethylketones.
V. Pace, G. Verniest, J.-V. Sinisterra, A. R. Alcántara, N. De Kimpe, J. Org. Chem., 2010, 75, 5760-5763.

The chain extension of carboxylic acids developed by Arndt and Eistert was applied to the construction of peptides containing β-amino acids. The method may be used for the generation of new types of peptide-containing combinatorial libraries.
J. Podlech, D. Seebach, Angew. Chem. Int. Ed., 1995, 34, 471-472.

Sonication of diazo ketones derived from Fmoc-protected amino acids in dioxane in the presence of silver benzoate and water results in clean formation of the corresponding β-amino acid derivatives. The degree of racemization was examined using capillary zone electrophoresis. No substantial epimerization occured except for phenylglycine.
A. Müller, C. Vogt, N. Sewald, Synlett, 2006, 837-841.