一价铜催化的N-对甲基苯磺酰腙与3-丁炔-1-醇的串联反应:一种四氢呋喃类化合物的新合成方法（英文）
发布时间：2019-05-07 22:25
【摘要】：最近几年来,利用稳定的重氮类化合物和N-对甲基苯磺酰腙类化合物作为金属卡宾前体,在过渡金属催化下通过形成金属卡宾的偶联反应引起了人们广泛的兴趣.金属卡宾前体与有机金属物种反应,可以生成金属卡宾中间体,并发生金属上基团的转移插入过程,得到新的有机金属物种,从而实现丰富的偶联反应.这类经由金属卡宾转移插入过程的交叉偶联反应为构建C C键,C N键以及许多环状化合物和不饱和有机分子结构提供了可靠而强有力的工具.本课题组一直致力于研究该类经由金属卡宾中间体的催化转化和偶联反应,报道了在铜催化下,对甲苯磺酰腙以及重氮类化合物可以与端炔反应,通过所形成的炔基铜卡宾中间体的转移插入过程,可高效得到联烯类化合物.该类反应条件相对温和,并且有很好的底物普适性.不仅各种多取代的联烯类化合物,而且苯并呋喃,菲以及呋喃等结构都可由这类铜催化的腙和炔烃的偶联反应来得到.在这些反应中,通过炔基铜卡宾中间体上炔基的转移插入过程,在形成了C(Sp3)-Cu键以后,通过铜的1,3-迁移过程,可以得到联烯结构,随后发生分子内杂原子的亲核进攻或者6π电子环化过程来实现苯并呋喃,菲等杂环类结构的构建.另一方面,该类反应进一步拓展和研究,可望得到其他有价值的有机分子骨架.环状的醚类结构,如四氢呋喃结构,也是有机化合物中常见的结构类型,我们希望从目前已经发展成熟的卡宾前体与炔烃生成联烯的偶联反应出发,通过分子内的串联过程来高效地构建取代的环状醚类结构.我们设想,在炔烃上引入氧原子作为亲核试剂,在形成联烯化合物以后,通过分子内氧原子对联烯基的亲核进攻,来实现串联的分子内关环反应,从而构建环状醚类结构.本文以CuI为催化剂,3-丁炔-1-醇为炔烃偶联组分,采用二芳基对甲苯磺酰腙作为金属卡宾前体,实现了取代四氢呋喃的合成.在对甲苯磺酰腙与3-丁炔-1-醇类化合物发生偶联反应生成二芳基联烯基化合物以后,采用一锅法实现分子内的关环反应,从而生成亚烯基取代的四氢呋喃化合物.该串联反应不仅具有原料易得和操作较为简便等优点,而且底物普适性和官能团耐受性都较好,多种取代的二芳基腙类化合物都能以较好的收率得到目标产物,从而为四氢呋喃类化合物的合成提供了一种新的方法.该反应进一步展示了经由金属卡宾中间体的交叉偶联反应的普遍性,将在有机化学和有机合成领域具有广泛的研究和应用价值.
[Abstract]:In recent years, stable diazo compounds and N-p-methylbenzenesulfonyl Hydrazone as precursors of metal carbene have attracted extensive interest through the formation of metal carbene coupling reactions under the catalysis of transition metals. The metal carbene precursor reacts with organometallic species to form metal carbene intermediates and the transfer insertion process of the groups on the metal to obtain new organometallic species thus realizing rich coupling reactions. These cross-coupling reactions via metal carbene transfer insertion provide a reliable and powerful tool for the construction of C C bond, C N bond and many cyclic and unsaturated organic molecular structures. Our team has been working on the catalytic conversion and coupling reactions of this kind of metal carbene intermediates. It is reported that p-toluenesulfonylhydrazone and diazodiazide can react with terminal alkynes under the catalysis of copper. Through the transfer and insertion process of the intermediate of alkynyl copper carbene, the dialkene compounds can be obtained efficiently. The reaction conditions are relatively mild and have good substrate universality. The structures of benzofuran, phenanthrene and furan can be obtained by the coupling reaction of Hydrazone and alkynes catalyzed by this kind of copper, not only many kinds of polysubstituted dienes, but also benzofuran, phenanthrene and furan. In these reactions, through the transfer and insertion of alkynyl groups on the copper carbene intermediates, after the formation of C (Sp3)-Cu bonds, through the 1,3-migration process of copper, the structure of the alkynes can be obtained. The heterocyclic structures of benzofuran, phenanthrene and other heterocyclic structures were constructed by nucleophilic attack or 6 蟺 electron cyclization of intramolecular heterocysts. On the other hand, this kind of reaction is further expanded and studied, and other valuable organic molecular skeletons are expected to be obtained. Cyclic ether structures, such as tetrahydrofuran structures, are also common structural types in organic compounds. We hope to start with the coupling reaction between carbene precursors and alkynes to form dienes, which are well developed at present. The substituted cyclic ethers are constructed efficiently by intramolecular tandem process. We assume that by introducing oxygen atoms into alkynes as nucleophilic reagents, after the formation of dienes, a series of intramolecular closed-ring reactions can be realized through the nucleophilic attack of intra-molecular oxygen atoms on the dienyl groups, so as to construct cyclic ethers. The synthesis of substituted tetrahydrofuran was carried out by using CuI as catalyst, 3-Butyne-1-alcohol as coupling component of alkynes and diaryl p-toluene sulfonylhydrazone as precursor of metal carbene. After the coupling reaction of p-toluenesulfonylhydrazone and 3-Butyne-1-alcohols to produce diaryl dienyl compounds, the intramolecular ring closing reaction was realized by one-pot method, and then the tetrahydrofuran compounds substituted by enenyl groups were formed. The series reaction not only has the advantages of easy to obtain raw materials and easy operation, but also has good substrate universality and functional group tolerance. Many substituted diaryl Hydrazone compounds can get the target products in good yield. This provides a new method for the synthesis of tetrahydrofuran compounds. This reaction further demonstrates the universality of the cross-coupling reaction via metal carbene intermediates, which will have extensive research and application value in the field of organic chemistry and organic synthesis.
【作者单位】： 北京大学化学与分子工程学院生物有机与分子工程教育部重点实验室北京分子科学国家实验室;中国科学院金属有机化学国家重点实验室;
【基金】：supported by the National Basic Research Program of China (973 Program, 2015CB856600) the National Natural Science Founda-tion of China (21472004, 21332002)~~
【分类号】：O621.251
[Abstract]:In recent years, stable diazo compounds and N-p-methylbenzenesulfonyl Hydrazone as precursors of metal carbene have attracted extensive interest through the formation of metal carbene coupling reactions under the catalysis of transition metals. The metal carbene precursor reacts with organometallic species to form metal carbene intermediates and the transfer insertion process of the groups on the metal to obtain new organometallic species thus realizing rich coupling reactions. These cross-coupling reactions via metal carbene transfer insertion provide a reliable and powerful tool for the construction of C C bond, C N bond and many cyclic and unsaturated organic molecular structures. Our team has been working on the catalytic conversion and coupling reactions of this kind of metal carbene intermediates. It is reported that p-toluenesulfonylhydrazone and diazodiazide can react with terminal alkynes under the catalysis of copper. Through the transfer and insertion process of the intermediate of alkynyl copper carbene, the dialkene compounds can be obtained efficiently. The reaction conditions are relatively mild and have good substrate universality. The structures of benzofuran, phenanthrene and furan can be obtained by the coupling reaction of Hydrazone and alkynes catalyzed by this kind of copper, not only many kinds of polysubstituted dienes, but also benzofuran, phenanthrene and furan. In these reactions, through the transfer and insertion of alkynyl groups on the copper carbene intermediates, after the formation of C (Sp3)-Cu bonds, through the 1,3-migration process of copper, the structure of the alkynes can be obtained. The heterocyclic structures of benzofuran, phenanthrene and other heterocyclic structures were constructed by nucleophilic attack or 6 蟺 electron cyclization of intramolecular heterocysts. On the other hand, this kind of reaction is further expanded and studied, and other valuable organic molecular skeletons are expected to be obtained. Cyclic ether structures, such as tetrahydrofuran structures, are also common structural types in organic compounds. We hope to start with the coupling reaction between carbene precursors and alkynes to form dienes, which are well developed at present. The substituted cyclic ethers are constructed efficiently by intramolecular tandem process. We assume that by introducing oxygen atoms into alkynes as nucleophilic reagents, after the formation of dienes, a series of intramolecular closed-ring reactions can be realized through the nucleophilic attack of intra-molecular oxygen atoms on the dienyl groups, so as to construct cyclic ethers. The synthesis of substituted tetrahydrofuran was carried out by using CuI as catalyst, 3-Butyne-1-alcohol as coupling component of alkynes and diaryl p-toluene sulfonylhydrazone as precursor of metal carbene. After the coupling reaction of p-toluenesulfonylhydrazone and 3-Butyne-1-alcohols to produce diaryl dienyl compounds, the intramolecular ring closing reaction was realized by one-pot method, and then the tetrahydrofuran compounds substituted by enenyl groups were formed. The series reaction not only has the advantages of easy to obtain raw materials and easy operation, but also has good substrate universality and functional group tolerance. Many substituted diaryl Hydrazone compounds can get the target products in good yield. This provides a new method for the synthesis of tetrahydrofuran compounds. This reaction further demonstrates the universality of the cross-coupling reaction via metal carbene intermediates, which will have extensive research and application value in the field of organic chemistry and organic synthesis.
【作者单位】： 北京大学化学与分子工程学院生物有机与分子工程教育部重点实验室北京分子科学国家实验室;中国科学院金属有机化学国家重点实验室;
【基金】：supported by the National Basic Research Program of China (973 Program, 2015CB856600) the National Natural Science Founda-tion of China (21472004, 21332002)~~
【分类号】：O621.251
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