- Pd/C-catalyzed synthesis of oxamates by oxidative cross double carbonylation of alcohols and tertiary amines through C-N bond cleavage
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An efficient synthesis of oxamates by Pd/C-catalyzed oxidative cross double carbonylation of alcohols and unactivated tertiary amines has been demonstrated. The in situ oxidative C-N bond cleavage of tertiary amines was achieved using molecular oxygen as an environmentally benign oxidant providing a user-friendly approach to the synthesis of oxamates. The developed protocol showed excellent activity towards the cyclic as well as aliphatic tertiary amines and long-chain alcohols. This developed protocol system is advantageous, as it is phosphine ligand free, base free, and copper-free and the Pd/C catalyst is easily recyclable. The Pd/C catalyst was recycled up to five consecutive cycles.
- Kolekar, Yuvraj A.,Bhanage, Bhalchandra M.
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p. 18072 - 18078
(2019/12/02)
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- Direct C?H Carbamoylation of Nitrogen-Containing Heterocycles
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Nucleophilic radical additions at innately electrophilic C(sp2) centers are perfectly suited for the direct functionalization of heterocycles. Using bench stable and commercially available alkyl oxamate and oxamic acid derivatives in combination with photoredox catalysis, a direct carbamoylation of heterocycles yielding amide functionalized pharmacophores in a single step is reported. The reaction conditions reported are compatible with structurally complex heterocyclic substrates of pharmaceutical interest. Notably, derivatives containing functional groups incompatible with standard amidation reactions, such as carboxylic acids and unprotected amines, were found to be amenable to this reaction paradigm.
- Jouffroy, Matthieu,Kong, Jongrock
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supporting information
p. 2217 - 2221
(2019/01/30)
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- Visible-light mediated carbamoyl radical addition to heteroarenes
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The generation of carbamoyl radicals, followed by their addition to heteroarenes, was performed under mild conditions through a metal-free photocatalyzed decarboxylation of oxamic acids. The process has been applied to the carbamoylation of heteroaromatic bases using α-aminoacid-derived oxamic acids, leading to the corresponding amides without racemization.
- Jatoi, Ashique Hussain,Pawar, Govind Goroba,Robert, Frédéric,Landais, Yannick
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supporting information
p. 466 - 469
(2019/01/10)
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- Metal-, Photocatalyst-, and Light-Free Direct C-H Acylation and Carbamoylation of Heterocycles
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Direct C-H acylations and carbamoylations of heterocycles can now be readily achieved without requiring any conventional metal, photocatalyst, electrocatalysis, or light activation, thus significantly improving on sustainability, costs, toxicity, waste, and simplicity of the operational procedure. These mild conditions are also suitable for gram-scale reactions and late-stage functionalizations of complex molecules, including pharmaceuticals, N,N-ligands, and light-sensitive molecules.
- Westwood, Matthew T.,Lamb, Claire J. C.,Sutherland, Daniel R.,Lee, Ai-Lan
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supporting information
p. 7119 - 7123
(2019/09/03)
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- An Improved Strategy for the Synthesis of Ethylene Glycol by Oxamate-Mediated Catalytic Hydrogenation
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The present study reports an improved approach for the preparation of ethylene glycol (EG) by using carbon monoxide as C1 chemical by a two-step oxidative carbonylation and hydrogenation sequence. In the first step, oxamates are synthesized through oxidative cross double carbonylation of piperidine and ethanol by using Pd/C catalyst under phosphine ligand-free conditions and subsequently hydrogenated by Milstein's catalyst (carbonylhydrido[6-(di-t-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyridine]ruthenium(II)). The presented stepwise oxamate-mediated coupling provides the basis for a new strategy for the synthesis of EG by selective upgrading of C1 chemicals.
- Satapathy, Anilkumar,Gadge, Sandip T.,Bhanage, Bhalchandra M.
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p. 1356 - 1359
(2017/04/14)
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- A model β-sheet interaction and thermodynamic analysis of β-strand mimetics
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β-Sheet mediated protein-protein interactions are involved in key signalling pathways in diseases such as cancer. We present small molecule β-strand mimetics and investigate their interactions with a model tripeptide. Using 1H NMR, the thermodynamic parameters for their binding are determined. These give insight into this biologically important interaction.
- Robinson, Colin W.,Rye, Carl S.,Chessum, Nicola E. A.,Jones, Keith
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supporting information
p. 7402 - 7407
(2015/07/15)
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- A model β-sheet interaction and thermodynamic analysis of β-strand mimetics
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β-Sheet mediated protein-protein interactions are involved in key signalling pathways in diseases such as cancer. We present small molecule β-strand mimetics and investigate their interactions with a model tripeptide. Using 1H NMR, the thermodynamic parameters for their binding are determined. These give insight into this biologically important interaction.
- Robinson, Colin W.,Rye, Carl S.,Chessum, Nicola E. A.,Jones, Keith
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supporting information
p. 7402 - 7407
(2015/11/27)
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- Mild gold-catalyzed aerobic dehydrogenative coupling of amines and phenylglyoxal derivatives
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A simple and efficient gold-catalyzed coupling of secondary amine with phenylglyoxal derivatives has been developed, which provides a practical synthetic strategy for the synthesis of substituted α-ketoamides under mild reaction conditions.
- Shao, Ying,Wu, Zhuhong,Miao, Chunbao,Liu, Li
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- Pd/C-catalyzed synthesis of oxamates by oxidative cross double carbonylation of amines and alcohols under Co-catalyst, base, dehydrating agent, and ligand-free conditions
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This work reports a mild, efficient, and ligand-free Pd/C-catalyzed protocol for the oxidative cross double carbonylation of amines and alcohols. Notably, the reaction does not requires any base, co-catalyst, dehydrating agent, or ligand. Pd/C solves the problem of catalyst recovery, and the catalyst was recycled up to six times.
- Gadge, Sandip T.,Bhanage, Bhalchandra M.
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p. 6793 - 6797
(2013/07/26)
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- Design, synthesis, structure, and acaricidal/insecticidal activity of novel spirocyclic tetronic acid derivatives containing an oxalyl moiety
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A series of novel spirocyclic tetronic acid derivatives containing an oxalyl moiety was designed and synthesized via the key intermediate 3-(2,4,6-trimethyl)-2-oxo-1-oxaspiro[4.4]-decyl-3-en-4-ol. The target compounds were identified by 1H NMR and elemental analysis or high-resolution mass spectrum (HRMS). The results of bioassays indicated that most of the target compounds possessed excellent acaricidal activities against carmine spider mite larvae and eggs. Especially, diisopropylamino oxalyl compound 7g and piperidine oxalyl compound 7h were 1.4- and 2.3-fold as high as the activities of commercial Spiromesifen, respectively, against spider mite eggs. Moreover, most of the target compounds exhibited insecticidal activities against Lepidoptera pest. Interestingly, compounds containing alkylamino-substituted oxalyl moiety showed obvious selectivity between spider mite larvae and eggs because the activities against spider mite eggs of 7g and 7h were 25-fold those against spider mite larvae, whereas Spiromesifen had no significant differences in these activities. This meant that the introduction of an oxalyl moiety to spirocyclic tetronic acid might lead to novel biological activity characteristics.
- Liu, Zhihui,Lei, Qiong,Li, Yongqiang,Xiong, Lixia,Song, Haibin,Wang, Qingmin
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experimental part
p. 12543 - 12549
(2012/03/10)
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- Synthesis and first X-ray structures of cobalt(II) and cobalt(III) complexes bearing 2,4-dioxo-alkanoic acid dialkylamide ligands
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The aerobic oxidation of 5-hydroxy pentenes to trans-tetrahydrofurans (THFs), the Mukaiyama oxidation, has in recent years emerged as a powerful tool in synthetic chemistry. In this report we describe the first crystal structures of 2,4-dioxo-alkanoic acid dialkylamide complexes for both Co(II) and Co(III) salts. The Co(II) structures show an unprecedented arrangement of atoms, with a central Co(II)(H2O)6 flanked by two Co(II) atoms each coordinated with three anionic chelating ligands. The dimeric Co(III) structures show two anionic chelating ligands and bridging hydroxyl groups.
- Wang, Jian,Morra, Nicholas A.,Zhao, Hongda,Gorman, Jeffrey S.T.,Lynch, Vincent,McDonald, Robert,Reichwein, John F.,Pagenkopf, Brian L.
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experimental part
p. 328 - 334
(2009/10/24)
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- Method of preparation of oxalic acid esters and amides
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A new process is described for the preparation of oxalic acid esters and amides of general formula (I) STR1 wherein Z designates an --OR or --NR1 R2 group, wherein R represents substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, R1 is hydrogen or substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, R2 represents substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, or R1 and R2 taken together with the adjacent nitrogen atom represent a saturated 5-, 6-, 7-, or 8-membered heterocyclic ring, which may contain an additional heteroatom selected from --O--, --S--, and --N(H, Alkyl)--, and optionally bear one or more alkyl or alkenyl substituents, and Z1 designates an --OR or --NR1 R2 group, wherein R, R1, and R2 are as defined before, or a group --NHCOCH3, which comprises the base-catalysed reaction of diacetyloxamide with an alcohol ROH or/and an amine HNR1 R2. The compounds of formula (I) have many industrial utilities, mainly as intermediates and stabilizers in the polymer field.
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- New method of preparation of oxalic acid esters and amides
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A new process is described for the preparation of oxalic acid esters and amides of general formula (I) Z- wherein, Z designates an -OR or -NR1R2 group, wherein R represents substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, R1 is hydrogen or substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, R2 represents substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, or aryl-alkyl, or R1 and R2 taken together with the adjacent nitrogen atom represent a saturated 5-, 6-, 7-, or 8-membered heterocyclic ring, which may contain an additional heteroatom selected from -O-, -S-, and -N(H, Alkyl)-, and optionally bear one or more alkyl or alkenyl substituents, and, Z1 designates an -OR or -NR1R2 group, wherein R, R1, and R2 are as defined before, or a group -NHCOCH3, which comprises the base-catalysed reaction of diacetyloxamide with an alcohol ROH or/and an amine HNR1R2. The compounds of formula (I) have many industrial utilities, mainly as intermediates and stabilizers in the polymer field.
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- Oxanilic acids, a new series of orally active antiallergic agents
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A large number of oxanilic acid esters and N heteroaryl oxamic acid esters were prepared and found to have antiallergic activity using the rat passive cutaneous anaphylaxis (PCA) test. Many of the oxanilic acid esters are active orally, with the most active species having an aryl 2' carbamoyl group and a 3' methoxy group. Hydrolysis of the ester from the oxanilic ester moiety causes a loss of oral activity.
- Sellstedt,Guinosso,Begany,Bell,Rosenthale
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p. 926 - 933
(2007/10/05)
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