3469-17-8Relevant articles and documents
The Generation of Carbene Anion Radicals from Diazo Compounds. Factors Influencing the Unimolecular Decomposition of the Anion Radicals of Diazo Compounds in Solution
Bethell, Donald,Parker, Vernon D.
, p. 7194 - 7200 (1986)
Anion radicals of two diazo compounds, azibenzil and diethyl diazomalonate, had previously been reported to undergo unimolecular decomposition in aprotic solvents to generate the corresponding carbene anion radicals.These processes have been examinated in detail by transient electrochemical techniques.The rate constants for the loss of dinitrogen in DMF at 273.2 K are 407 and 125 s-1 for the anion radicals of diethyl diazomalonate and azibenzil, respectively.There is little difference in the rate constants in the two solvents.The activation enthalpies fall in the range 10.6-12.7 kcal/mol, and the entropies of activation are close to -6 cal/(K*mol).Hydrogen bonding to water (i) (Ki = 0.8 M-1) facilitates unimolecular decomposition. The hydrogen bonded complex, Ph(PhCO)C=N2.-/HOH, undergoes first-order decomposition with a rate constant in acetonitrile at 273.2 K equal to 1700 s-1.This rate enhancement is attributed to the localization of charge away from nitrogen.The carbonyl group adjacent to the diazo function in both substrates also facilitates loss of dinitrogen.It is concluded that unimolecular loss of nitrogen is a more favorable process than previously thought, especially at higher temperatures and when the charge is delocalized.
Reactions of α-diazoketones with indolinone imines: Synthesis of new 1,3,3-triaryl-1′-methylspiro[azetidine-2,3′-indoline]-2′, 4-diones
Singh, Girija S.,Mmolotsi, Boycie J.
, p. 1665 - 1668 (2006)
The paper describes the synthesis of new 1,3,3-triary-1′- methylspiro[azetidine-2,3′-indoline]-2′,4-diones from reaction of the 2-diazo-1,2-diarylethanones with 3-arylimino-1-methyl-2-indolinones. The compounds have been characterized by satisfactory anal
Bis-Rhodamines Bridged with a Diazoketone Linker: Synthesis, Structure, and Photolysis
Belov, Vladimir N.,Bossi, Mariano L.,Hell, Stefan W.,Shojaei, Heydar
, p. 56 - 65 (2022/01/03)
Two fluorophores bound with a short photoreactive bridge are fascinating structures and remained unexplored. To investigate the synthesis and photolysis of such dyes, we linked two rhodamine dyes via a diazoketone bridge (?COCN2?) attached to p
Gold-Catalyzed [3+2]-Annulations of α-Aryl Diazoketones with the Tetrasubstituted Alkenes of Cyclopentadienes: High Stereoselectivity and Enantioselectivity
Chen, Ching-Nung,Cheng, Wei-Min,Wang, Jian-Kai,Chao, Tzu-Hsuan,Cheng, Mu-Jeng,Liu, Rai-Shung
supporting information, p. 4479 - 4484 (2021/01/21)
This work reports gold-catalyzed [3+2]-annulations of α-diazo ketones with highly substituted cyclopentadienes, affording bicyclic 2,3-dihydrofurans with high regio- and stereoselectivity. The reactions highlights the first success of tetrasubstituted alkenes to undergo [3+2]-annulations with α-diazo carbonyls. The enantioselective annulations are also achieved with high enantioselectivity using chiral forms of gold and phosphoric acid. Our mechanistic analysis supports that cyclopentadienes serve as nucleophiles to attack gold carbenes at the more substituted alkenes, yielding gold enolates that complex with chiral phosphoric acid to enhance the enantioselectivity.
Blue Light-Promoted N?H Insertion of Carbazoles, Pyrazoles and 1,2,3-Triazoles into Aryldiazoacetates
Stivanin, Mateus L.,Fernandes, Alessandra A. G.,da Silva, Amanda F.,Okada, Celso Y.,Jurberg, Igor D.
supporting information, p. 1106 - 1111 (2020/01/25)
Blue light irradiation of aryldiazoacetates leads to the formation of free carbenes, which can react with carbazoles, pyrazoles and 1,2,3-triazoles to afford the corresponding N?H inserted products. These reactions are performed under air and at room temperature, allowing the mild preparation of a variety of motifs found in biologically relevant targets. (Figure presented.).
Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
, p. 3000 - 3010 (2017/03/23)
An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
Alkyl halide-free heteroatom alkylation and epoxidation facilitated by a recyclable polymer-supported oxidant for the in-flow preparation of diazo compounds
Nicolle, Simon M.,Hayes, Christopher J.,Moody, Christopher J.
supporting information, p. 4576 - 4579 (2015/03/18)
Highly reactive metal carbenes, generated from simple ketones via diazo compounds, including diazoamides and -phosphonates, using a recyclable reagent inflow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only byproducts being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds.
Enantioselective N-H insertion reaction of α-aryl α-diazoketones: An efficient route to chiral α-aminoketones
Xu, Bin,Zhu, Shou-Fei,Zuo, Xiao-Dong,Zhang, Zhi-Chao,Zhou, Qi-Lin
supporting information, p. 3913 - 3916 (2014/05/06)
A highly enantioselective N-H insertion reaction of α-diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α-aminoketones, which are versatile building blocks in organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions. Spiro inspiration: A highly enantioselective N-H insertion reaction of α-diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α-aminoketones, which are versatile building blocks in the organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions.
Potassium N-iodo p-toluenesulfonamide (TsNIK, iodamine-T): A new reagent for the oxidation of hydrazones to diazo compounds
Nicolle, Simon M.,Moody, Christopher J.
supporting information, p. 4420 - 4425 (2014/05/06)
A new reagent for the oxidation of hydrazones to diazo compounds is described. N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T) allows the preparation of α-diazoesters, α-diazoamides, α-diazoketones and α-diazophosphonates in good yield and in high purity after a simple extractive work-up. α-Diazoesters were also obtained in high yield from the corresponding ketones through a one-pot process of hydrazone formation/oxidation. Diazo compounds: N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T), readily prepared from p-toluenesulfonamide and iodine in aqueous KOH, is a new reagent for the oxidation of hydrazones to diazo compounds in good yields and high purity (see scheme).
Synthesis of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition
Jiang, Yaojia,Khong, Vanessa Zhong Yue,Lourdusamy, Emmanuvel,Park, Cheol-Min
experimental part, p. 3133 - 3135 (2012/05/04)
An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.
