脯氨酸衍生的氮杂环卡宾（NHC）-金属络合物的合成及应用
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摘要
本论文主要从天然手性的脯氨酸出发,合成其衍生的氮杂环卡宾(NHC)钯,铑金属络合物,并对这些络合物的催化性能进行了研究。我们还合成了一类新型的氮杂环卡宾(NHC)-钯(Ⅱ)-咪唑(Im)络合物并对其催化性能进行了研究。本论文主要可以分为以下几部分：
一、我们以良好的收率成功地合成了脯氨酸衍生的NHC-Pd(Ⅱ)络合物,其结构都得到了X-ray单晶衍射的确认。研究表明,吡咯环骨架氮原子上的取代基对钯络合物的结构有很大的影响。比如：氮原子上为供电子的Bn基团时,其结构是以金属钯为中心,吡咯环氮原子和卡宾碳原子参与配位形成C-Pd-N双齿NHC-Pd(Ⅱ)络合物；而当氮原子上为吸电子的Ts基团时,则吡咯环氮原子不参与配位,形成的是二聚单齿NHC-Pd(Ⅱ)络合物。
二、脯氨酸衍生的NHC-Pd(Ⅱ)络合物在C-C键形成中的应用。在水相介质中,此类NHC-Pd(Ⅱ)络合物可以高效地催化溴、碘代芳烃的Suzuki-Miyaura偶联反应和Mizoroki-Heck反应,并且都能以优良的产率得到偶联产物。
三、我们合成了脯氨酸衍生的NHC-Rh(Ⅰ)络合物,并且成功应用于催化芳基硼酸与α,β-不饱和羰基化合物的1,4-共轭加成反应中,在水相介质中40℃下,可以得到良好到优异的产率
四、我们使用IPr·HCl或IMes·HCl与氯化钯,1-甲基咪唑为原料合成了一种新型的NHC-Pd(Ⅱ)-Im络合物,并且高效地催化了氯代芳烃与芳基酸的Suzuki-Miyaura偶联反应。当催化量降为0.01mol%,投料扩大到20 mmol时仍然能够得到相当的产率。这部分工作在附录中介绍。
The thesis mainly focused on the synthesis of N-heterocyclic carbene (NHC)-palladium and rhodium complexes derived from L-proline and their catalytic activity in carbon-carbon bond formations. In addition, novel well-defined NHC-Pd-Im complexes were synthesized and their catalytic activities in Suzuki-Miyaura coupling of aryl chlorides were investigated. The thesis can be divided into the following parts:
1. NHC-Pd(II) complexes derived from proline have been successfully synthesized in good yields and their structures have been characterized by X-ray single crystal diffraction. It was found that the substituents on the N-atom of the pyrrolidine skeleton dramatically affect on the coordination pattern of the palladium complexes. In a word, when an electron-rich group such as benzyl group was attached on the//-atom, both of the N-atom and NHC were coordinated to the Pd(II) center; while when an electron-poor group such as Ts group was attached, a dimeric mono-coordinated Pd(II)-NHC was obtained exclusively.
2. Applications of NHC-Pd(II) complexes derived from proline in carbon-carbon bond formations were carried out and it was found that the complexes are highly effective catalyst in Suzuki-Miyaura and Mizoroki-Heck reactions of aryl iodides and bromides performed in neat water.
3. Novel NHC-Rh(I) complexes derived from N-benzyl substituted proline have been successfully synthesized and were found to be efficient catalysts for the 1,4-conjugate addition of arylboronic acids to enones in neat water at 40℃. Under the optimal reaction conditions, all reactions gave the addition products in good to high yields.
4. A new type of well-defined NHC-palladium chloride-imidazole complexes was synthesized from readily available starting materials as IPrHCl or IMes'HCl with PdCl2 and 1-methylimidazole. These air-and moisture stable NHC-Pd(II)-Im complexes exhibit high catalytic activity in the Suzuki-Miyaura coupling reactions of aryl or heteroaryl chlorides. Moreover, the large-scale (20.0 mmol) couplings in the presence of 0.01 mol% catalyst loading can also give the corresponding coupling products in high yields. These contents are displayed in the Appendix.
一、我们以良好的收率成功地合成了脯氨酸衍生的NHC-Pd(Ⅱ)络合物,其结构都得到了X-ray单晶衍射的确认。研究表明,吡咯环骨架氮原子上的取代基对钯络合物的结构有很大的影响。比如：氮原子上为供电子的Bn基团时,其结构是以金属钯为中心,吡咯环氮原子和卡宾碳原子参与配位形成C-Pd-N双齿NHC-Pd(Ⅱ)络合物；而当氮原子上为吸电子的Ts基团时,则吡咯环氮原子不参与配位,形成的是二聚单齿NHC-Pd(Ⅱ)络合物。
二、脯氨酸衍生的NHC-Pd(Ⅱ)络合物在C-C键形成中的应用。在水相介质中,此类NHC-Pd(Ⅱ)络合物可以高效地催化溴、碘代芳烃的Suzuki-Miyaura偶联反应和Mizoroki-Heck反应,并且都能以优良的产率得到偶联产物。
三、我们合成了脯氨酸衍生的NHC-Rh(Ⅰ)络合物,并且成功应用于催化芳基硼酸与α,β-不饱和羰基化合物的1,4-共轭加成反应中,在水相介质中40℃下,可以得到良好到优异的产率
四、我们使用IPr·HCl或IMes·HCl与氯化钯,1-甲基咪唑为原料合成了一种新型的NHC-Pd(Ⅱ)-Im络合物,并且高效地催化了氯代芳烃与芳基酸的Suzuki-Miyaura偶联反应。当催化量降为0.01mol%,投料扩大到20 mmol时仍然能够得到相当的产率。这部分工作在附录中介绍。
The thesis mainly focused on the synthesis of N-heterocyclic carbene (NHC)-palladium and rhodium complexes derived from L-proline and their catalytic activity in carbon-carbon bond formations. In addition, novel well-defined NHC-Pd-Im complexes were synthesized and their catalytic activities in Suzuki-Miyaura coupling of aryl chlorides were investigated. The thesis can be divided into the following parts:
1. NHC-Pd(II) complexes derived from proline have been successfully synthesized in good yields and their structures have been characterized by X-ray single crystal diffraction. It was found that the substituents on the N-atom of the pyrrolidine skeleton dramatically affect on the coordination pattern of the palladium complexes. In a word, when an electron-rich group such as benzyl group was attached on the//-atom, both of the N-atom and NHC were coordinated to the Pd(II) center; while when an electron-poor group such as Ts group was attached, a dimeric mono-coordinated Pd(II)-NHC was obtained exclusively.
2. Applications of NHC-Pd(II) complexes derived from proline in carbon-carbon bond formations were carried out and it was found that the complexes are highly effective catalyst in Suzuki-Miyaura and Mizoroki-Heck reactions of aryl iodides and bromides performed in neat water.
3. Novel NHC-Rh(I) complexes derived from N-benzyl substituted proline have been successfully synthesized and were found to be efficient catalysts for the 1,4-conjugate addition of arylboronic acids to enones in neat water at 40℃. Under the optimal reaction conditions, all reactions gave the addition products in good to high yields.
4. A new type of well-defined NHC-palladium chloride-imidazole complexes was synthesized from readily available starting materials as IPrHCl or IMes'HCl with PdCl2 and 1-methylimidazole. These air-and moisture stable NHC-Pd(II)-Im complexes exhibit high catalytic activity in the Suzuki-Miyaura coupling reactions of aryl or heteroaryl chlorides. Moreover, the large-scale (20.0 mmol) couplings in the presence of 0.01 mol% catalyst loading can also give the corresponding coupling products in high yields. These contents are displayed in the Appendix.
引文
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48. The crystal data of complex 9a has been deposited in CCDC with number 761757. Empirical Formula:C16H21Br2N3Pd; Formula Weight: 521.58; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic Lattice Type: Primitive; Lattice Parameters:a= 9.2705(13)A, b= 14.1816(19)A, c = 13.7065(18)A, α= 90°, β= 102.129(2)°, γ= 90°, V= 1761.8(4)A3; Space group:P 21/c; Z= 4; Dcalc= 1.966 g/cm3; F000= 1016; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0288,0.0768. 49. The crystal data of complex 9b has been deposited in CCDC with number 761753. Empirical Formula:C17H23Br2N3Pd; Formula Weight:535.60; Crystal Color, Habit: colorless, prismatic; Crystal System:Monoclinic; Lattice Type:Primitive; Lattice Parameters:a= 9.6028(9)A,b= 14.5618(13)A, c= 13.8519(13)A, α= 90°, β= 102.888(2)°, γ= 90°, V= 1888.2(3)A3; Space group:P2(1)/c; Z= 4; Dcalc= 1.884 g/cm3; F000= 1048; Difiractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0464,0.1122.
50. The crystal data of 9c has been deposited in CCDC with number 782957. Empirical Formula: C18H25Br2N3Pd; Formula Weight: 549.63; Crystal Color, Habit: colorless, prismatic; Crystal System: Orthorhombic; Lattice Type: Primitive; Lattice Parameters:a= 9.8678(4) A, b= 13.8740(6)A, c= 14.7557(6)A, α= 90°, β= 90°, γ-90°, V= 2020.14(15)A3; Space group:P2(1)2(1)2(1); Z= 4; Dcalc= 1.807 g/cm3; F000= 1080; Diffractometer: Bruker Smart APEX CCD; Residuals:R; Rw:0.0182,0.0443.
51. Flahaut A., Baltaze J.-P., Roland S., Mangeney P. Synthesis of chiral imino-and amino-imidazolium salts and of chelating amino-N-heterocyclic carbene palladium(II) complexes [J]. J. Org. Chem.2006, 691(16),3498-3508.
52. The crystal data of 10 has been deposited in CCDC with number 761755. Empirical Formula: C16H23Cl2N3OPd; Formula Weight: 450.67; Crystal Color, Habit: colorless, prismatic; Crystal System: Orthorhombic; Lattice Type: Primitive; Lattice Parameters:a= 8.5445(6)A, b= 13.6489(9)A, c= 15.6269(10)A, α= 90°, β= 90°, γ= 90°, V= 1822.5(2)A3; Space group:P212121; Z= 4; Dcalc= 1.643 g/cm3; F000= 912; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0326,0.0746.
53. The crystal data of 11 has been deposited in CCDC with number 761758. Empirical Formula: 2; Formula Weight:998.03; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic; Lattice Type: Primitive; Lattice Parameters:a= 10.3040(8)A, b= 24.1974(19)A, c= 18.9602(15)A, α= 90°, β°= 102.979(2)°, γ= 90°, V= 4606.6(6)A3; Space group:P 21/n; Z= 4; Dcalc= 1.439 g/cm3; F000= 1964; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0913,0.2376.
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84. The crystal data of 7a has been deposited in CCDC with number 795265. Empirical Formula: C31H42Cl2N4Pd; Formula Weight: 647.99; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic; Lattice Type: Primitive; Lattice Parameters:a=9.7912(7)A, b=22.6920(17)A, c= 14.8396(11)A, α= 90°, β= 98.950(2)°, γ= 90°, V= 3256.9(4)A3; Space group: P2(1)/c; Z=4; Dcalc= 1.321 g/cm3; F000= 1344; Diffractometer: Bruker Smart APEX CCD; Residuals: R; Rw: 0.0426,0.0688.
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48. The crystal data of complex 9a has been deposited in CCDC with number 761757. Empirical Formula:C16H21Br2N3Pd; Formula Weight: 521.58; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic Lattice Type: Primitive; Lattice Parameters:a= 9.2705(13)A, b= 14.1816(19)A, c = 13.7065(18)A, α= 90°, β= 102.129(2)°, γ= 90°, V= 1761.8(4)A3; Space group:P 21/c; Z= 4; Dcalc= 1.966 g/cm3; F000= 1016; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0288,0.0768. 49. The crystal data of complex 9b has been deposited in CCDC with number 761753. Empirical Formula:C17H23Br2N3Pd; Formula Weight:535.60; Crystal Color, Habit: colorless, prismatic; Crystal System:Monoclinic; Lattice Type:Primitive; Lattice Parameters:a= 9.6028(9)A,b= 14.5618(13)A, c= 13.8519(13)A, α= 90°, β= 102.888(2)°, γ= 90°, V= 1888.2(3)A3; Space group:P2(1)/c; Z= 4; Dcalc= 1.884 g/cm3; F000= 1048; Difiractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0464,0.1122.
50. The crystal data of 9c has been deposited in CCDC with number 782957. Empirical Formula: C18H25Br2N3Pd; Formula Weight: 549.63; Crystal Color, Habit: colorless, prismatic; Crystal System: Orthorhombic; Lattice Type: Primitive; Lattice Parameters:a= 9.8678(4) A, b= 13.8740(6)A, c= 14.7557(6)A, α= 90°, β= 90°, γ-90°, V= 2020.14(15)A3; Space group:P2(1)2(1)2(1); Z= 4; Dcalc= 1.807 g/cm3; F000= 1080; Diffractometer: Bruker Smart APEX CCD; Residuals:R; Rw:0.0182,0.0443.
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52. The crystal data of 10 has been deposited in CCDC with number 761755. Empirical Formula: C16H23Cl2N3OPd; Formula Weight: 450.67; Crystal Color, Habit: colorless, prismatic; Crystal System: Orthorhombic; Lattice Type: Primitive; Lattice Parameters:a= 8.5445(6)A, b= 13.6489(9)A, c= 15.6269(10)A, α= 90°, β= 90°, γ= 90°, V= 1822.5(2)A3; Space group:P212121; Z= 4; Dcalc= 1.643 g/cm3; F000= 912; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0326,0.0746.
53. The crystal data of 11 has been deposited in CCDC with number 761758. Empirical Formula: 2; Formula Weight:998.03; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic; Lattice Type: Primitive; Lattice Parameters:a= 10.3040(8)A, b= 24.1974(19)A, c= 18.9602(15)A, α= 90°, β°= 102.979(2)°, γ= 90°, V= 4606.6(6)A3; Space group:P 21/n; Z= 4; Dcalc= 1.439 g/cm3; F000= 1964; Diffractometer:Bruker Smart APEX CCD; Residuals:R; Rw:0.0913,0.2376.
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84. The crystal data of 7a has been deposited in CCDC with number 795265. Empirical Formula: C31H42Cl2N4Pd; Formula Weight: 647.99; Crystal Color, Habit: colorless, prismatic; Crystal System: Monoclinic; Lattice Type: Primitive; Lattice Parameters:a=9.7912(7)A, b=22.6920(17)A, c= 14.8396(11)A, α= 90°, β= 98.950(2)°, γ= 90°, V= 3256.9(4)A3; Space group: P2(1)/c; Z=4; Dcalc= 1.321 g/cm3; F000= 1344; Diffractometer: Bruker Smart APEX CCD; Residuals: R; Rw: 0.0426,0.0688.
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