10264-14-9Relevant academic research and scientific papers
A novel solid-phase chlorinating reagent for the synthesis of acyl chlorides
Luo, Guanglin,Xu, Li,Poindexter, Graham S.
, p. 8909 - 8912 (2002)
Cyanuric chloride was loaded onto a modified Wang resin, which was successfully used to convert carboxylic acids to their corresponding acyl chlorides. The formation of acyl chlorides were confirmed by condensation with various amines or alcohols to form the corresponding amides or esters.
Aminolysis of Triphenylantimony Dicarboxylates and Its Application to Catalytic Amidation
Nomura, Ryoki,Wada, Takao,Yamada, Yasuhiro,Matsuda, Haruo
, p. 1901 - 1904 (1986)
Triphenylantimony dicarboxylates (Ph3Sb(O2CR)2, where R=Me, CF3, Ph and CH2NH-Z) readily reacted with amines (R'NH2, where R'=n-C6H13, s-Bu, C6H11, and Ph) to afford corresponding amides and triphenylstibine oxide in fairly good yields.The amidation of RCO2H with R'NH2 was also catalyzed by the organoantimony compounds.
A mild and general solid-phase method for the synthesis of chiral polyamines. Solution studies on the cleavage of borane-amine intermediates from the reduction of secondary amides
Manku,Laplante,Kopac,Chan,Hall
, p. 874 - 885 (2001)
A mild oxidative workup protocol using iodine in an acetic acid-acetate buffer solution is described for the cleavage of borane-amine adducts arising from the borane-promoted reduction of polyamides supported onto practical trityl-based resins. Chiral polyamines with diverse side-chain functionalities can be generated as free bases without premature release from the solid support and with essentially no racemization using this method. A series of model oligomeric secondary diamides 6 containing various α-amino acid residues (Val, Phe, Tyr, Ser, Cys, Met, Gln, Trp) provided triamine products 8 in high yields and good to excellent purity. On the other hand, a substrate containing a tertiary amide (15) formed a rather unusual triaminoborane intermediate that required more stringent workup conditions to liberate the polyamine product 20. The reduction of oligomeric tertiary amides such as 9 was found sluggish, but these compounds could nonetheless be obtained in high purity from in situ reductive amination of the corresponding secondary amines. Control studies, carried out in solution with model secondary amide 23, confirmed the efficiency of the buffered iodine solution and highlighted several advantages (no heating necessary, no need for strong bases or acids) over existing methods for the cleavage of borane-amine adducts. A possible mechanism involving all buffer components (iodine, acetic acid, and acetate ion) is proposed in which borane-amine adducts are transformed first to the monoiodoborane-amine and then to the corresponding acetoxyborane-amine adduct of much weaker coordination affinity. The latter would dissociate readily and get trapped by the acetic acid to provide the desired secondary amine. This reduction/oxidative workup protocol is useful as a general method for the facile solid-phase synthesis of polyamines for eventual release in solution and use in various applications. It is also potentially very useful toward the synthesis and screening of bead-supported libraries of free oligoamines assembled through split-pool methods.
Preparation, structure, and reactivity of bicyclic benziodazole: A new hypervalent iodine heterocycle
Jarvi, Melissa E.,Makitalo, Cody L.,Rohde, Gregory T.,Saito, Akio,Shea, Michael T.,Yoshimura, Akira,Yusubov, Mekhman S.,Zhdankin, Viktor V.
, p. 1016 - 1020 (2018)
A new bicyclic organohypervalent iodine heterocycle derivative of benziodazole was prepared by oxidation of 2-iodo-N,N'-diiso-propylisophthalamide with m-chloroperoxybenzoic acid under mild conditions. Single crystal X-ray crystallography of this compound revealed a five-membered bis-heterocyclic structure with two covalent bonds between the iodine atom and the nitrogen atoms. This novel benziodazole is a very stable compound with good solubility in common organic solvents. This compound can be used as an efficient reagent for oxidatively assisted coupling of carboxylic acids with alcohols or amines to afford the corresponding esters or amides in moderate yields.
Zirconium-catalyzed direct amide bond formation between carboxylic esters and amines
Lenstra, Danny C.,Nguyen, D. Thao,Mecinovi?, Jasmin
, p. 5547 - 5553 (2015)
Development of catalytic amide bond formation reactions from readily available starting materials remains a challenging task for modern organic chemistry. Herein, we report that unactivated carboxylic esters and amines react in the presence of 10 mol % of zirconocene dichloride (Cp2ZrCl2) in toluene at 110 °C to afford amides in very good to excellent conversions. The Zr-catalyzed reaction is amenable for the amidation of aliphatic and aromatic carboxylic esters with primary and secondary amines. The reaction proceeds with almost complete retention of configuration for chiral esters and chiral amines.
Chemoselective calcium-catalysed direct amidation of carboxylic esters
Nguyen, D. Thao,Lenstra, Danny C.,Mecinovi?, Jasmin
, p. 77658 - 77661 (2015)
Unactivated carboxylic esters and primary amines undergo calcium-catalysed direct amide bond formation in excellent yields under homogeneous conditions in toluene. This green and mild reaction proceeds chemoselectively with esters, whereas related carboxylic acids and amides remain unreactive.
Organocatalytic and enantioselective [4+2] cyclization between hydroxymaleimides and: Ortho -hydroxyphenyl para -quinone methide-selective preparation of chiral hemiketals
Xiang, Min,Li, Chen-Yi,Song, Xiang-Jia,Zou, Ying,Huang, Zhi-Cheng,Li, Xia,Tian, Fang,Wang, Li-Xin
, p. 14825 - 14828 (2020)
A cinchona alkaloid squaramide promoted enantioselective [4+2] cyclization between hydroxymaleimides and ortho-hydroxyphenyl p-QMs has been disclosed, and a wide range of chiral hemiketals containing chromane and succinimide frameworks with two adjacent quaternary stereogenic centers have been prepared for the first time with excellent results (up to 99% yield, up to 99?:?1 dr, up to >99% ee) under mild conditions. This journal is
Mechanistic studies into metal-catalyzed aldoxime to amide rearrangements
Allen, C. Liana,Lawrence, Ruth,Emmett, Liam,Williams, Jonathan M. J.
, p. 3262 - 3268 (2011)
The metal-catalyzed rearrangement of aldoximes into primary amides is a completely atom economical synthetic method for the preparation of one of the most important functional groups in chemistry. There have been several reports of various metals successfully catalyzing this reaction, however, there are conflicting views as to the mechanism involved. Herein we report new experimental evidence to support the mechanism and whether this is universal to all catalysts reported or metal specific. We also describe our further studies into the mechanism of the nickel-catalyzed acylation of amines with aldoximes. Copyright
Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides
Boyle, Mhairi,Livingstone, Keith,Henry, Martyn C.,Elwood, Jessica M. L.,Lopez-Fernandez, J. Daniel,Jamieson, Craig
supporting information, p. 334 - 338 (2022/01/20)
We report how the rearrangement of highly reactive nitrile imines derived from N-2-nitrophenyl hydrazonyl bromides can be harnessed for the facile construction of amide bonds. This amidation reaction was found to be widely applicable to the synthesis of primary, secondary, and tertiary amides and was used as the key step in the synthesis of the lipid-lowering agent bezafibrate. The orthogonality and functional group tolerance of this approach was exemplified by the N-acylation of unprotected amino acids.
N -Heterocyclic carbene (NHC) catalyzed amidation of aldehydes with amines via the tandem N -hydroxysuccinimide ester formation
Singh, Ashmita,Narula
supporting information, p. 7486 - 7490 (2021/05/13)
A facile method for the amidation of aldehydes by a cascade approach was developed. This methodology, reported for the first time, uses a N-heterocyclic carbene (NHC) as the catalyst, and N-hydroxysuccinimide (NHS) mediated synthesis of amides utilising TBHP as the oxidant. Various substituted aldehydes reacted smoothly with NHS giving the corresponding active esters in moderate to good yields, which facilely converted into amides in one pot. In addition, the drug moclobemide was synthesized to represent the practical utility of the developed methodology. This journal is
