钯催化炔烃的卤钯化反应和偶联反应的研究
摘要
本论文主要研究了钯催化炔烃的卤钯化反应和偶联反应及钯催化的其它偶联反应。主要研究内容如下：
1．对钯催化炔烃的卤钯化反应、自偶联反应和交叉偶联反应的进展作了综述。从捕捉炔烃的卤钯化反应中间体角度详细地介绍了炔烃的卤钯化反应和从配体、催化剂、反应介质三个方面详细地介绍了交叉偶联反应，另外还介绍了炔烃的卤钯化反应和交叉偶联反应的机理。
2．发展了两个在卤化钯／卤化铜的催化体系中的炔烃卤钯化反应：(1)钯催化末端炔烃高效地和选择性地反应生成(Z，Z)-1，4-二卤-1，3-二烯，在这个反应中溶剂对选择性有关键的影响；(2)钯选择性催化邻炔基苯酚环化合成2-取代的3-卤苯并呋喃，在此反应中添加剂三乙胺氢卤酸盐对选择性起到关键作用。
3．发展了卤化铜作用的邻乙炔基苯甲酸酯环化反应选择性地得到相应的卤代异香豆素和以氯化铁为催化剂催化邻乙炔基苯甲酸酯环化选择性地合成异香豆素。
4．分别研究了在无膦配体和无胺的条件下的钯催化末端炔烃的自偶联反应和Dabco促进的钯催化末端炔烃的自偶联反应。
5．研究了炔烃在三种不同催化体系中的交叉偶联反应：(1)在醋酸钯和Dabco的作用下，实现了空气氛中和不添加铜盐无配体的钯催化Sonogashira反应；(2)PdCl_2(PPh_3)_2和TBAF在无溶剂的条件下能快速地催化芳香卤与末端炔烃发生交叉偶联反应：(3)(E)-1，2-二碘烯烃与末端炔烃反应可选择性地合成不对称1，3-丁二炔，通过简单的加热反式1，2-二碘烯烃与邻羟基苯乙炔可一步合成2-乙炔基苯并呋喃。
6．研究了三种钯催化的偶联反应：(1)Pd(OAc)_2/Dabco和Pd(dba)_2/AB-Cy分别有效地催化Stille交叉偶联反应：(2)在离子液体中无配体钯催化的Suzuki交叉偶联反应；(3)氯化铵促进在水溶剂中的钯催化芳基溴的Ullmann自偶联反应。
This thesis is concerned with studying the halopalladation reactionand coupling reaction of alkynes as well as some palladium-catalyzedcoupling reactions. The main contents are included:
1. The progress in the palladium-catalyzed halopalladation reaction,cross-coupling reaction and homo-coupling reaction of alkynes aresummarized. The halopalladation reactions of alkynes were firstlyintroduced in detail from the view of trapping the intermediate ofhalopalladation of alkynes. Subsequently, the Sonogashiracross-coupling reactions of alkynes were also described based onligands, catalysts and reaction media. Noteworthy is that themechanisms of the palladium-catalyzed halopalladation reaction andthe Sonogashira reactions of alkynes were also introduced.
2. Two types of halopalladation reactions of alkynes using PdCl_2/CuCl_2catalystic system have been developed including: the regioselectiveand stereoselective palladium-catalyzed dimerizations of terminalalkynes method for the synthesis of symmetrical(Z,Z)-1,4-dihalo- 1,3-dienes, and the palladium-catalyzed armulationsof 2-alkynylphenols method for the synthesis of 2-substituted3-halobenzo[b]furans. The results showed that the selectivity of the fore reaction based on the solvent, and the selectivity of the latterreaction was controlled by the HEt_3NX additives.
3. Both CuX_2-mediated the annulation reactions ofo-(alk-1-ynyl)benzoates by to synthesize the corresponding4-haloisocoumarins and FeCl_3-catalyzed cyclization ofo-(alk-1-ynyl)benzoates to synthesize 3-substituted isocoumarins werepresented, respectively.
4. Two protocols for the palladium-catalyzed homocoupling reactions ofterminal alkynes have demonstrated using thePd(OAc)_2/CuI/DABCO/air system or the PdCl_2/CuI/NaOAc/Me_3NOsystem.
5. The Sonogashira reactions were studied under three different reactionconditions. Firstly, Pd(OAc)_2 combined with Dabco was found to bean efficient catalytic system for the mild and aerobic Sonogashiracross-coupling reactions under copper- and ligand-free conditions.Secondly, a general and fast Sonogashira cross-coupling reaction wasprovided using PdCl_2(PPh_3)_2 as the catalyst and TBAF as the baseunder solvent-free conditions. Finally, the palladium-catalyzedcross-coupling reactions of terminal alkynes with(E)-1,2-diiodoalkenes were developed for the synthesis ofunsymmetrical 1,3-butadiynes and 2-ethynylphenol with(E)-1,2-diiodoalkenes for the synthesis of 2-ethynylbenzofurans in one-pot by simple heating using Pd(OAc)_2/CuI catalytic system.
6. Three kinds of palladium-catalyzed coupling reactions were studiedincluding: (1) the Stille cross-coupling reactions using thePd(OAc)_2/Dabco catalytic system or the Pd(dba)_2/DAB-Cy catalyticsystem, (2) the ligand-free palladium-catalyzed Suzuki cross-couplingreaction in ionic liquid, and (3) the ammonium chloride-promotedpalladium-catalyzed Ullmann coupling reactions of aryl bromides inwater.
1．对钯催化炔烃的卤钯化反应、自偶联反应和交叉偶联反应的进展作了综述。从捕捉炔烃的卤钯化反应中间体角度详细地介绍了炔烃的卤钯化反应和从配体、催化剂、反应介质三个方面详细地介绍了交叉偶联反应，另外还介绍了炔烃的卤钯化反应和交叉偶联反应的机理。
2．发展了两个在卤化钯／卤化铜的催化体系中的炔烃卤钯化反应：(1)钯催化末端炔烃高效地和选择性地反应生成(Z，Z)-1，4-二卤-1，3-二烯，在这个反应中溶剂对选择性有关键的影响；(2)钯选择性催化邻炔基苯酚环化合成2-取代的3-卤苯并呋喃，在此反应中添加剂三乙胺氢卤酸盐对选择性起到关键作用。
3．发展了卤化铜作用的邻乙炔基苯甲酸酯环化反应选择性地得到相应的卤代异香豆素和以氯化铁为催化剂催化邻乙炔基苯甲酸酯环化选择性地合成异香豆素。
4．分别研究了在无膦配体和无胺的条件下的钯催化末端炔烃的自偶联反应和Dabco促进的钯催化末端炔烃的自偶联反应。
5．研究了炔烃在三种不同催化体系中的交叉偶联反应：(1)在醋酸钯和Dabco的作用下，实现了空气氛中和不添加铜盐无配体的钯催化Sonogashira反应；(2)PdCl_2(PPh_3)_2和TBAF在无溶剂的条件下能快速地催化芳香卤与末端炔烃发生交叉偶联反应：(3)(E)-1，2-二碘烯烃与末端炔烃反应可选择性地合成不对称1，3-丁二炔，通过简单的加热反式1，2-二碘烯烃与邻羟基苯乙炔可一步合成2-乙炔基苯并呋喃。
6．研究了三种钯催化的偶联反应：(1)Pd(OAc)_2/Dabco和Pd(dba)_2/AB-Cy分别有效地催化Stille交叉偶联反应：(2)在离子液体中无配体钯催化的Suzuki交叉偶联反应；(3)氯化铵促进在水溶剂中的钯催化芳基溴的Ullmann自偶联反应。
This thesis is concerned with studying the halopalladation reactionand coupling reaction of alkynes as well as some palladium-catalyzedcoupling reactions. The main contents are included:
1. The progress in the palladium-catalyzed halopalladation reaction,cross-coupling reaction and homo-coupling reaction of alkynes aresummarized. The halopalladation reactions of alkynes were firstlyintroduced in detail from the view of trapping the intermediate ofhalopalladation of alkynes. Subsequently, the Sonogashiracross-coupling reactions of alkynes were also described based onligands, catalysts and reaction media. Noteworthy is that themechanisms of the palladium-catalyzed halopalladation reaction andthe Sonogashira reactions of alkynes were also introduced.
2. Two types of halopalladation reactions of alkynes using PdCl_2/CuCl_2catalystic system have been developed including: the regioselectiveand stereoselective palladium-catalyzed dimerizations of terminalalkynes method for the synthesis of symmetrical(Z,Z)-1,4-dihalo- 1,3-dienes, and the palladium-catalyzed armulationsof 2-alkynylphenols method for the synthesis of 2-substituted3-halobenzo[b]furans. The results showed that the selectivity of the fore reaction based on the solvent, and the selectivity of the latterreaction was controlled by the HEt_3NX additives.
3. Both CuX_2-mediated the annulation reactions ofo-(alk-1-ynyl)benzoates by to synthesize the corresponding4-haloisocoumarins and FeCl_3-catalyzed cyclization ofo-(alk-1-ynyl)benzoates to synthesize 3-substituted isocoumarins werepresented, respectively.
4. Two protocols for the palladium-catalyzed homocoupling reactions ofterminal alkynes have demonstrated using thePd(OAc)_2/CuI/DABCO/air system or the PdCl_2/CuI/NaOAc/Me_3NOsystem.
5. The Sonogashira reactions were studied under three different reactionconditions. Firstly, Pd(OAc)_2 combined with Dabco was found to bean efficient catalytic system for the mild and aerobic Sonogashiracross-coupling reactions under copper- and ligand-free conditions.Secondly, a general and fast Sonogashira cross-coupling reaction wasprovided using PdCl_2(PPh_3)_2 as the catalyst and TBAF as the baseunder solvent-free conditions. Finally, the palladium-catalyzedcross-coupling reactions of terminal alkynes with(E)-1,2-diiodoalkenes were developed for the synthesis ofunsymmetrical 1,3-butadiynes and 2-ethynylphenol with(E)-1,2-diiodoalkenes for the synthesis of 2-ethynylbenzofurans in one-pot by simple heating using Pd(OAc)_2/CuI catalytic system.
6. Three kinds of palladium-catalyzed coupling reactions were studiedincluding: (1) the Stille cross-coupling reactions using thePd(OAc)_2/Dabco catalytic system or the Pd(dba)_2/DAB-Cy catalyticsystem, (2) the ligand-free palladium-catalyzed Suzuki cross-couplingreaction in ionic liquid, and (3) the ammonium chloride-promotedpalladium-catalyzed Ullmann coupling reactions of aryl bromides inwater.
引文
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