作者机构:
[Qun Cai; Fengcheng Jia; Jiachen Xiang; Yanping Zhu; Anxin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry,Central China Normal University Hubei
摘要:
In recent years,the direct coupling of the C-H bond has emerged as an ideal method for the formation of carbon–carbon(C–C)and carbon–heteroatom(C–X)bonds.This approach,due to its substantial benefits for organic synthesis,has garnered significant attention from the chemical community.[1] Many impressive results have been achieved with C-H bond coupling through methods,such as C-H activation,cross-dehydrogenative coupling,and radical coupling,among others.[2] Carboline derivatives are known as one of the most important and abundant heterocycles.Compounds containing carboline corn structures are of great pharmaceutical interest due to their potent biological activity and medicinal significance.In particular,the privileged scaffold β-carboline skeleton widely exists in various natural products and “drug-like”small molecules.In this context,we present a cascade coupling protocol for the synthesis of β-carboline derivatives from acetophenone and tryptophan.The mechanistic pathway involved iodination,Kornblum oxidation,Pictet-Spengler condensation,and decarboxylation.
作者机构:
[Jia-Chen Xiang; Qing-He Gao; Yan-Ping Zhu; An-Xin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry,Central China Normal University Hubei
会议名称:
中国化学会第29届学术年会
会议时间:
2014-08-04
会议地点:
北京
关键词:
diverted total synthesis;iodination;kornblum oxidation
摘要:
Where much past research has focused upon structural complexity,a major contemporary line of inquiry of synthetic chemists focuses on maximizing efficiency and minimizing steps in total synthesis.Among which,diverted total synthesis[1](DTS)is highly valued in the synthesis of natural products and analogues because it achieves both structural complexity and diversity.According to this,we envisioned that an in situ trapping version of DTS approach containing in situ generated intermediates including common precursors and trapping process in one pot to achieve natural products with diversity promise higher efficiency and practicality in total synthesis.For examples,as common precursors,aromatic α-keto aldehydes were generated in situ via the indination and kornblum oxidation reaction sequence from acetophenone then further trapped by amino acids,benzylamine,tryptamine and 2-aminobenzamide and eventually approached to the family of Pimprinine,Uguenenazole,Eudistomins Y1-Y7 and Luotonin F,respectively.[2]
摘要:
The term “self-sorting”has been discussed extensively during the past decade in chemistry.[1] Usually,“sorting”is defined as a process in which different subunits are controlled with precise constitutional and/or positional order according to certain features or criteria.Thus “self-sorting”refers to not only the ability to distinguish “self”from “nonself”,but also the operation completed simultaneously and orthogonally within the mixtures.[2] Intuitively,self-sorting phenomena are very common in biological systems and complex supramolecular systems but rare in synthetic systems.[3] Based on the self-sorting property of molecular clusters,we have proposed a novel synthetic strategy of self-sorting reaction systems,which could also be described as multi-domino routes converging strategy.We have developed an efficient carbon-carbon double bond-forming reaction via homo-coupling of aryl methyl ketones or hetreo-coupling of methyl ketones with β-ketone esters and have investigated novel synthetic methods for some structurally diverse heterocyclic library via self-sorting domino strategy.[4]
作者机构:
[Qinghe Gao; Xia Wu; Shan Liu; Anxin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R.China
摘要:
Transition metal-catalyzed reactions for the direct functionalization of C-H bonds,especially sp3 C-H bonds for the construction of carbon-carbon and carbon-heteroatom bonds,has provided a great impetus to modern organic synthesis.1 Iodine catalyzed C-H bond functionalization reactions,which are driven by radical-and in situ iodination-based pathways,have recently been used in the successful development of complementary methods for the direct activation of C-H bonds.2 Despite these recent advances,research towards the development of iodine catalyzed methods for the direct functionalization of C-H bonds is still in its infancy,and plenty of opportunities still exist to further explore this fascinating area.In contrast to ketones,esters,3 and oxindoles,4 reports pertaining to the direct functionalization of theα-Csp3-H bonds of simple amides remain scarce,5 most likely because of the high pKa values(pKa>35 in DMSO)of amideα-C-H bonds[6]and the potential for the formation of by-products.
作者机构:
[Wen-Ming Shu; Jun-Rui Ma; An-Xin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry,Central China Normal University
会议名称:
中国化学会第29届学术年会
会议时间:
2014-08-04
会议地点:
北京
会议论文集名称:
中国化学会第29届学术年会摘要集-第07分会:有机化学
关键词:
Cyclopropanes;One-Pot;Three-Component.
摘要:
Cyclopropane unit as a fundamental structure performs a key role in a wide range of natural products as well as biological active molecules.[1] Because of the importance of cyclopropanes, enormous effort has therefore been devoted to this activity, and considerable methods have been developed for the construction of cyclopropane derivatives.[2] Generally, this small and highly strained skeleton is established by the addition of a carbine to an electron-deficient olefin.[3] In addition, Michael-initiated ring-closure procedures are also good approaches for the synthesis of multifunctionalized cyclopropanes.[4] In this communication we describe a one-pot three-component process for the synthesis of polyfunctional cyclopropanes.
摘要:
A novel method for constructing trisubstituted imidazoles has been created using simple and readily available aromatic ketones, benzoins, and ammonium acetate as starting materials. The new synthetic strategy utilized a convergent integration of two self-labor domino sequences, providing a typical example for logical self-organization synthesis. (C) 2013 Elsevier Ltd. All rights reserved.
作者机构:
[Xia Wu; Qing-He Gao; Mi Lian; Shan Liu; An-Xin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R.China
摘要:
The a-hydroxy carbonyl moiety is an important structural unit that is widely found in drug molecules,natural products and as a potentially valuable synthetic intermediate in organic and medicinal chemistry.Due to this,there have been many reports of synthetic methodologies for the construction ofα-hydroxy carbonyl compounds.However,in these transformations,few methods have been developed for direct oxidation of olefins approach to a-hydroxy ketones,due to the difficulty in introducing two oxygen atoms concurrently and oxidizing selectively.Molecule iodine as an old reagentas has been widely used in organic synthesis for various organic functional group conversions due to its various functionalizing abilities and low cost,nontoxicity and easy availability.Over the past few years,iodine-catalysed reactions have been increasingly explored.In particular,the molecule iodine activation of carbon-carbon double bonds has received widespread interest in recent years.In general,initial activation of theπ-bond can be achieved either through a charge transfer complex or via an iodonium/iodonium intermediate.Subsequently,it could be attacked by a intermolecular nucleophile or intramolecular nucleophile to yield the respective target compounds.To the best of our knowledge,a method for the I2-promoted direct activation and oxidation of styrenes toα-hydroxyacetophenones has not been reported as yet.In this paper,an iodine-promoted activation of carbon-carbon double bonds is depicted to synthesizeα-hydroxyacetophenones.
摘要:
<正>Introduction The term"self-sorting"has been discussed extensively during the past decade in chemistry.Usually,"sorting"is defined as a process in which different subunits are controlled with precis
作者机构:
[Feng-Cheng Jia; Qun Cai; An-Xin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry,Central China Normal University
会议名称:
中国化学会第29届学术年会
会议时间:
2014-08-04
会议地点:
北京
关键词:
one-pot;iodine;domino reaction;deacylation
摘要:
1,2-dihydrobenzo[e][1,2,4]triazine is a important class of heterocycles,which exists widely in natural products.Many compounds containing those motifs exhibit potent biological activities and medicinal significance.Herein we developed a highly efficient I2 promoted domino protocol for the diverse synthesis of highly substituted 1,2-dihydrobenzo[e][1,2,4]triazines from simple and readily available aryl methyl ketones and N'-(2-aminophenyl)benzohydrazides.In our reaction,three mechanism-different reactions(iodination,[1] Kornblum oxidation,[2] and heterocyclization)were assembled in a single reactor.[3-5] Hydrazine hydrate could be used as nucleophilic agent to attack the carbonyl group of product A to produce another product B,which underwent a deacylation process.[6] It is notable that the reaction performs well with varying functional group tolerance in the absence of any metal,base,or ligand.Due to the above mentioned characteristics of this reaction,it should be of great utility for concise construction of diverse heterocycles for organic chemistry and medicinal chemistry.
作者机构:
[Shu,Wen-Ming; Ma,Jun-Rui; Wu,An-Xin] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University,Wuhan 430079
会议名称:
中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会
会议时间:
2013-10-17
会议地点:
重庆
会议主办单位:
中国化学会;重庆市科协
会议论文集名称:
中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会论文集
关键词:
one-pot;3-pyrrolin-2-ones;1,4-enedione
摘要:
The 3-pyrrolin-2-ones are of great important class of heterocyclic compounds, and found in several natural products[1]. They and their derivatives exhibit wide range of biological and pharmacological
作者机构:
[Gao,Qinghe; Wu,Xia; Zhu,Yanping; Wu,Anxin] Key Laboratory of Pesticide & Chemical Biology,Ministry of Education,College of Chemistry,Central China Normal University,Wuhan 430079
会议名称:
中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会
会议时间:
2013-10-17
会议地点:
重庆
会议主办单位:
中国化学会;重庆市科协
会议论文集名称:
中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会论文集
关键词:
one-pot synthesis of natural products;sp3 C-H functionalization;oxazoles
摘要:
The direct C-H bond functionalization,especially sp3 C-H bond functionalization for the construction of carbon-carbon and carbon-heteroatom bond has become an important synthetic strategy.In recent ye
作者:
Tao Pang;Qinwan Yang;Yu Sun;Meng Wang;Anxin Wu
作者机构:
[Tao Pang; Qinwan Yang; Yu Sun; Meng Wang; Anxin Wu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079,China
会议名称:
全国第十六届大环化学暨第八届超分子化学学术讨论会
会议时间:
2012-10-27
会议地点:
扬州
会议主办单位:
中国化学会
会议论文集名称:
全国第十六届大环化学暨第八届超分子化学学术讨论会论文集
关键词:
one-pot;macrocycles;coordination processes
摘要:
<正>The high significance of macrocyclic structures is not only in drug development,but also in areas as diverse as material sciences and supramolecular chemistry.Herein,we reported a new efficient met
摘要:
Two new glycoluril derivatives, namely 6-phenyl-1,4-dioxo-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a-pentaazacyclopenta[cd]indene-2a,7b-dicarboxylate (1), and diethyl 6-(2,4-dichorophenyl)-1,4-dioxo-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a-pentaazacyclopenta[cd]indene-2a,7b-dicarboxylate (2) have been synthesized and structurally determined by X-ray diffraction analysis. Compound 1 is, monoclinic, space group C2/c, with a = 20.0784(7), b = 9.0316(3), c = 23.0980(8) Å, β = 98.3930(10), V = 4143.7(2) Å3, with Z = 8 for d
calc = 1.338 Mg/m3. The analog 2 is, Triclinic, space group P-1, with a = 8.9353(18), b = 10.466(2), c = 14.679(3) Å, β = 73.60(3), V = 1268.1(4) Å3, with Z = 2 for d
calc = 1.533 Mg/m3. X-ray analysis reveals that both glycoluril derivatives bearing two free syn-urea NH groups and two ureidyl C=O, assemble the same one-dimensional chains in the solid-state running parallel to the [110], [1–10] and [010] directions via N–H···O hydrogen bonds. Two new glycoluril derivatives, namely 6-phenyl-1,4-dioxo-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a-pentaazacyclopenta[cd]indene-2a,7b-dicarboxylate (1), and diethyl 6-(2,4-dichorophenyl)-1,4-dioxo-2,2a,3,4,6,7-hexahydro-1H,5H-2,3,4a,6,7a-pentaazacyclopenta[cd]indene-2a,7b-dicarboxylate (2), both bearing two free syn-urea NH groups and two ureidyl C=O, assemble the same one-dimensional chains in the solid-state running parallel to the [110], [1–10] and [010] directions via R
2
2
(8) N–H···O hydrogen bonds.