149142-51-8Relevant articles and documents
Synthesis of acyl fluorides via photocatalytic fluorination of aldehydic C-H bonds
Meanwell, Michael,Lehmann, Johannes,Eichenberger, Marc,Martin, Rainer E.,Britton, Robert
, p. 9985 - 9988 (2018/09/11)
Acyl fluorides are versatile acylating agents owing to their unique stability. Their synthesis, however, can present challenges and is typically accomplished through deoxyfluorination of carboxylic acids. Here, we demonstrate that acyl fluorides can be prepared directly from aldehydes via a C(sp2)-H fluorination reaction involving the inexpensive photocatalyst sodium decatungstate and electrophilic fluorinating agent N-fluorobenzenesulfonimide. This convenient fluorination strategy enables direct conversion of aliphatic and aromatic aldehydes into acylating agents.
Specificity of DNA alkylation by 1-(2-chloroethyl)-3-alkyl-3- acyltriazenes depends on the structure of the acyl group: Kinetic and product studies
Smith,Schmidt,Czerwinski,Taneyhill,Snyder,Kline,Michejda,Smith Jr.
, p. 466 - 475 (2007/10/03)
The reactions of calf thymus DNA with ten 1-(2-chloroethyl)-3-alkyl-3- acyltriazenes of varying acyl side chain structure were studied alone, or in the presence of porcine liver esterase in pH 7.0 phosphate buffer. In several of the key triazenes, the acyl substituent contained a free carboxylic acid group. With esterase present in the reaction mixture, the resultant levels of DNA alkylation could be correlated with the kinetic rates of decomposition of the triazenes. Under these conditions, the predominant pathway of decomposition involved deacylation of the parent triazene and eventual production of an alkanediazonium ion. This intermediate subsequently alkylated DNA-guanine to give 7-alkylguanine as the principal reaction product. In the absence of esterase, the order of DNA alkylation for all of the acyltriazenes did not correlate with their respective rates of decomposition, leading to the conclusion that the triazenes did not decompose by the expected mode of uncatalyzed N(2)-N(3) heterolyic cleavage. The major DNA alkylation product from the N(3)-methyltriazenes was 7-methylguanine, instead of the expected 7-(chloroethyl)- and 7-(hydroxyethyl)guanine products, which suggested that the acyl group was being hydrolyzed. However, acyltriazenes with an N(3)-benzyl group rather than a methyl in this position produced very little 7-benzylguanine product, contrary to prediction. An alternative mechanism involving internally assisted hydrolysis of the side chain ester is proposed to explain these results. NMR product analysis and computational studies were carried out to lend support to the postulated mechanism.
Novel Efficient Synthesis of 1-Ethoxyvinyl Esters Using Ruthenium Catalysts and Their Use in Acylation of Amines and Alcohols: Synthesis of Hydrophilic 3'-N-Acylated Oxaunomycin Derivatives
Kita, Yasuyuki,Maeda, Hiroshi,Omori, Kana,Okuno, Takayuki,Tamura, Yasumitsu
, p. 2999 - 3006 (2007/10/02)
A novel and efficient synthesis of 1-ethoxyvinyl esters 3a-i from carboxylic acids 4a-i and ethoxyacetylene 5 by using a catalytic amount of ruthenium complex 2> 6f has been developed.These reagents reacted smoothly with amines and alcohols to give the corresponding N- and O-acylated compounds in excellent yields.This acylation method has been applied to the synthesis of hydrophilic 3'-N-acylated oxaunomycin derivatives 13a,b.
