一價銅催化的N-對甲基苯磺酰腙與3-丁炔-1-醇的串聯(lián)反應:一種四氫呋喃類化合物的新合成方法（英文）
發(fā)布時間：2019-05-07 22:25
【摘要】：最近幾年來,利用穩(wěn)定的重氮類化合物和N-對甲基苯磺酰腙類化合物作為金屬卡賓前體,在過渡金屬催化下通過形成金屬卡賓的偶聯(lián)反應引起了人們廣泛的興趣.金屬卡賓前體與有機金屬物種反應,可以生成金屬卡賓中間體,并發(fā)生金屬上基團的轉移插入過程,得到新的有機金屬物種,從而實現(xiàn)豐富的偶聯(lián)反應.這類經(jīng)由金屬卡賓轉移插入過程的交叉偶聯(lián)反應為構建C C鍵,C N鍵以及許多環(huán)狀化合物和不飽和有機分子結構提供了可靠而強有力的工具.本課題組一直致力于研究該類經(jīng)由金屬卡賓中間體的催化轉化和偶聯(lián)反應,報道了在銅催化下,對甲苯磺酰腙以及重氮類化合物可以與端炔反應,通過所形成的炔基銅卡賓中間體的轉移插入過程,可高效得到聯(lián)烯類化合物.該類反應條件相對溫和,并且有很好的底物普適性.不僅各種多取代的聯(lián)烯類化合物,而且苯并呋喃,菲以及呋喃等結構都可由這類銅催化的腙和炔烴的偶聯(lián)反應來得到.在這些反應中,通過炔基銅卡賓中間體上炔基的轉移插入過程,在形成了C(Sp3)-Cu鍵以后,通過銅的1,3-遷移過程,可以得到聯(lián)烯結構,隨后發(fā)生分子內(nèi)雜原子的親核進攻或者6π電子環(huán)化過程來實現(xiàn)苯并呋喃,菲等雜環(huán)類結構的構建.另一方面,該類反應進一步拓展和研究,可望得到其他有價值的有機分子骨架.環(huán)狀的醚類結構,如四氫呋喃結構,也是有機化合物中常見的結構類型,我們希望從目前已經(jīng)發(fā)展成熟的卡賓前體與炔烴生成聯(lián)烯的偶聯(lián)反應出發(fā),通過分子內(nèi)的串聯(lián)過程來高效地構建取代的環(huán)狀醚類結構.我們設想,在炔烴上引入氧原子作為親核試劑,在形成聯(lián)烯化合物以后,通過分子內(nèi)氧原子對聯(lián)烯基的親核進攻,來實現(xiàn)串聯(lián)的分子內(nèi)關環(huán)反應,從而構建環(huán)狀醚類結構.本文以CuI為催化劑,3-丁炔-1-醇為炔烴偶聯(lián)組分,采用二芳基對甲苯磺酰腙作為金屬卡賓前體,實現(xiàn)了取代四氫呋喃的合成.在對甲苯磺酰腙與3-丁炔-1-醇類化合物發(fā)生偶聯(lián)反應生成二芳基聯(lián)烯基化合物以后,采用一鍋法實現(xiàn)分子內(nèi)的關環(huán)反應,從而生成亞烯基取代的四氫呋喃化合物.該串聯(lián)反應不僅具有原料易得和操作較為簡便等優(yōu)點,而且底物普適性和官能團耐受性都較好,多種取代的二芳基腙類化合物都能以較好的收率得到目標產(chǎn)物,從而為四氫呋喃類化合物的合成提供了一種新的方法.該反應進一步展示了經(jīng)由金屬卡賓中間體的交叉偶聯(lián)反應的普遍性,將在有機化學和有機合成領域具有廣泛的研究和應用價值.
[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.
【作者單位】： 北京大學化學與分子工程學院生物有機與分子工程教育部重點實驗室北京分子科學國家實驗室;中國科學院金屬有機化學國家重點實驗室;
【基金】：supported by the National Basic Research Program of China (973 Program, 2015CB856600) the National Natural Science Founda-tion of China (21472004, 21332002)~~
【分類號】：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.
【作者單位】： 北京大學化學與分子工程學院生物有機與分子工程教育部重點實驗室北京分子科學國家實驗室;中國科學院金屬有機化學國家重點實驗室;
【基金】：supported by the National Basic Research Program of China (973 Program, 2015CB856600) the National Natural Science Founda-tion of China (21472004, 21332002)~~
【分類號】：O621.251
【相似文獻】
相關期刊論文 前10條
1 劉榕芳,肖秀峰,朱則善;消耗鎂陽極在羰基還原偶聯(lián)反應中的應用[J];精細化工;2000年S1期
2 辛炳煒;;水相中Suzuki偶聯(lián)反應研究進展[J];德州學院學報;2007年04期
3 夏文娟;潘劍明;陳波;馬銀標;;三叔丁基膦在偶聯(lián)反應中的應用[J];浙江冶金;2009年04期
4 許華建;，
本文編號：2471407
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2471407.html
最近更新
教材專著
