基于联萘骨架的氮杂环卡宾配体的金属钯和金络合物的合成及应用
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摘要
本论文主要围绕由联萘胺衍生的氮杂环卡宾配体及其金属钯和金络合物的合成,以及这些金属络合物在均相催化反应中的应用而展开。
1双齿双氮杂环卡宾的钯络合物的合成及其应用
从光学纯的联萘胺出发,合成了一系列带有不同阴离子配体和N-取代基的轴手性氮杂环卡宾配体的二价钯络合物I-la,b,I-2a-d, I-3a和I-4a-h,它们的结构均通过NMR、MS和IR等表征,其中络合物Ⅰ-4c的结构还经过X-Ray单晶衍射分析的确认。
这些氮杂环卡宾的二价钯络合物能够有效地催化二乙基锌诱导极性反转的醛的不对称烯丙基化反应。金属钯中心的阴离子配体X会明显改变反应的速率,而反应的对映选择性则会受到N-CH2R取代基和阴离子X的共同影响。其中,N-CH2R的R为平面的苯基和X为溴离子的钯络合物I-4b是最好效果的催化剂。对于芳香醛和脂肪醛底物,均可取得58-96%的收率,54-66%ee的对映选择性,以及高达syn:anti> 99:1的非对映选择性。
2氮杂环卡宾和氮给体的混合配体及其金属钯络合物的合成与表征
从光学纯的联萘胺出发,合成了四个氮杂环卡宾和氮给体混合配体的钯络合物,即氮杂环卡宾-磺酰胺的Ⅱ-7,氮杂环卡宾-水杨醛亚胺的Ⅱ-14,氮杂环卡宾-苯甲醛亚胺的Ⅱ-18,以及氮杂环卡宾-胺基的Ⅱ-19。
它们的结构均通过NMR、MS和IR等表征,其中络合物Ⅱ-7、Ⅱ-14和Ⅱ-18的结构还经过X-Ray单晶衍射分析的确认。在金属钯周围,络合物Ⅱ-7、Ⅱ-14和Ⅱ-18均表现为三齿螯合的配位方式,而络合物Ⅱ-19则可能是由氮杂环卡宾与胺基两齿螯合在钯中心的结构。
3双齿双氮杂环卡宾的二价钯络合物在烯烃双氧化反应中的应用
以PhI(OAc)2作为促进PdⅡ/PdⅣ催化循环的氧化剂,在耐空气和水气的温和条件下,氮杂环卡宾的二价钯络合物能够成功地催化烯烃的双氧化反应,其中,阳离子的钯络合物Ⅰ-2d表现出最高的催化活性。对于1,2-双取代的烯烃底物,它们的双氧化反应能够取得良好的顺式非对映选择性；而对于苯乙烯类衍生物,则会得到其1,2-和1,l-双氧化的混合产物,其中,富电子的衍生物有利于1,1-双氧化产物的生成。
另外,通过同位素标记实验,我们还对该反应PdⅡ/PdⅣ催化循环的机理做了相应的研究,从而对各种产物的分配比例和非对映选择性做出了合理的解释。
4单齿氮杂环卡宾配体的金络合物的合成及其应用
从光学纯的联萘胺出发,合成了一系列单齿氮杂环卡宾配体的金络合物Ⅳ-1,Ⅳ-2a,b和Ⅳ-3-11,它们的结构经过了核磁、质谱和红外等的表征。其中,络合物Ⅳ-1,Ⅳ-2a和Ⅳ-6的结构还得到X-Ray单晶衍射分析的确认,它们的卡宾碳原子和阴离子配体在金的周围均表现为近似直线形的配位方式。
这些氮杂环卡宾的金络合物能够有效地催化联烯-醇Ⅳ-47的分子内环化反应,在室温下能以优秀的收率得到相应的醚产物,但是反应的手性诱导效果(up to 24% ee)却并不理想。
这些氮杂环卡宾的金络合物也能高效地催化1,6-烯炔的分子内环化反应,反应均能以很快的速率顺利进行。其中,络合物Ⅳ-6是最好的催化剂,在0°C下,以最高>99%的收率和59%ee的对映选择性得到相应的乙酰氧基环化产物Ⅳ-50a。
以Ph2SO作为氧化剂,氮杂环卡宾的金络合物还能高效地催化1,6-烯炔的氧化重排反应,这实际上是捕获到了金催化1,6-烯炔重排过程中的五元环并三元环的金卡宾中间体B。其中,络合物Ⅳ-2a是最好的催化剂,在10°C下,以最高达>99%的收率和65%ee的对映选择性得到相应的醛产物Ⅳ-53。
This thesis was mainly focused on the synthesis of N-heterocyclic carbene (NHC) ligands derived from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and their palladium(Ⅱ) and gold(Ⅰ) complexes, and applications of these complexes in the catalytic transformations.
1 Synthesis and application of bidentate bis(NHC)-Pd(Ⅱ) complexes
A series of axially chiral bis(NHC)-Pd(II) complexes I-la,b, I-2a-d, I-3a and I-4a-h bearing different coordinating counterions and N-substituents have been prepared from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and fully characterized by NMR, MS and IR spectroscopies et al.. The structure of complex I-4c was also confirmed by its single-crystal X-ray diffraction study.
These bis(NHC)-Pd(II) complexes as catalysts were effective in Et2Zn-mediated enantioselective umpolung allylation of aldehydes with cyclohexenyl acetate. While the variation of coordinating anion counterions may significantly change the raction rate, the enantioselectivity was both affected by coordinating counterions on palladium center and N-substituents around the N-heterocycle. For both aromatic and aliphatic aldehydes, complex I-4b bearing bromide counterions and N-CH2Ph substituents was the best catalyst to afford the homoallylic alcohol products in moderate to excellent yields (58%-96%), modest enantioselcetivities (54%-66% ee), and good to excellent syn diastereoselectivities (up to> 99:1 dr).
2 Synthesis and characterization of palladium(Ⅱ) complexes of chelating NHC-N donor hybrid ligands
A new class of palladium(Ⅱ) complexes of chelating NHC-N donor hybrid ligands such as NHC-sulfonamide (Ⅱ-7), NHC-phenoxyimine (Ⅱ-14), NHC-phenylimine (Ⅱ-18) and NHC-amine (Ⅱ-19) have been successfully synthesized in modest yields from optically pure 1,1'-binaphthyl-2,2'-diamine (BINAM).
These complexes have been characterized by all NMR, MS and IR spectroscopic data. The structures of II-7,11-14 and 11-18 were also confirmed by single-crystal X-ray diffraction studies to exhibit tridentate chelating motifs around the palladium center, but complexⅡ-19 was proposed to comprise a bidentate chelating NHC-amine hybrid ligand and two bromide counterions.
3 Bidentate bis(NHC)-palladium(II) complex-catalyzed dioxygenation of alkenes
Bis(NHC)-palladium(II) complex were successfully used to catalyze the dioxygenation of alkenes under mild conditions tolerant of air and moisture, by using PhI(OAc)2 as the oxidant for its PdⅡ/PdⅣcatalytic cycle. Cationic NHC-Pd2+ diaquo complexⅠ-2d exhibited the highest catalytic activity to give 1,2-dioxygenation products with good syn-diastereoselectivity for 1,2-disubstituted alkenes, but styrene derivatives often afforded both 1,2- and 1,1-dioxygenation products with electron-rich derivatives being more liable to form the 1,1-dioxygenation product.
By isotopic labeling experiments, we also investigated the possible mechanism involving PdⅡ/PdⅣcatalytic cycle to reasonably reveal the distribution of different products and their diastereoselectivities.
4 Synthesis and applications of monodentate NHC-Au(I) complexes
A series of axially chiral NHC-Au(I) complexesⅣ-1,Ⅳ-2a,b and IV-3-11 have been successfully synthesized from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and fully characterized by NMR, MS and IR spectroscopies et al. The structures of complexesⅣ-1,Ⅳ-2a andⅣ-6 were also confirmed by single-crystal X-ray diffraction studies, exhibiting a nearly linear coordination geometry of NHC and anion counterion ligands around gold center.
These NHC-Au(I) complexes could effectively catalyze the intramolecular hydroalkoxylation of allenes to afford the ether product. in excellent yields but with unsatisfactory low enantioselectivities (up to 24% ee).
These NHC-Au(I) complexes as catalysts were successfully applied in the intramolecular cyclization of 1,6-enynes. ComplexⅣ-6 was examined to be the best catalyst giving the acetoxyl productⅣ-50a in up to>99% yield and 59% ee under 0℃condition.
The oxidative rearrangement of 1,6-enynes could also proceed smoothly with these NHC-Au(Ⅰ) complexes as catalysts by using Ph2SO as the oxidant, which is in fact the interception of cyclopropane gold(I)-carbenoid intermediate B for the gold(I)-catalyzed rearrangement of 1,6-enyne. ComplexⅣ-2a afforded the best results of up to>99% yield and 65% ee for the corresponding aldehyde productⅣ-53 under the condition of 10℃.
1双齿双氮杂环卡宾的钯络合物的合成及其应用
从光学纯的联萘胺出发,合成了一系列带有不同阴离子配体和N-取代基的轴手性氮杂环卡宾配体的二价钯络合物I-la,b,I-2a-d, I-3a和I-4a-h,它们的结构均通过NMR、MS和IR等表征,其中络合物Ⅰ-4c的结构还经过X-Ray单晶衍射分析的确认。
这些氮杂环卡宾的二价钯络合物能够有效地催化二乙基锌诱导极性反转的醛的不对称烯丙基化反应。金属钯中心的阴离子配体X会明显改变反应的速率,而反应的对映选择性则会受到N-CH2R取代基和阴离子X的共同影响。其中,N-CH2R的R为平面的苯基和X为溴离子的钯络合物I-4b是最好效果的催化剂。对于芳香醛和脂肪醛底物,均可取得58-96%的收率,54-66%ee的对映选择性,以及高达syn:anti> 99:1的非对映选择性。
2氮杂环卡宾和氮给体的混合配体及其金属钯络合物的合成与表征
从光学纯的联萘胺出发,合成了四个氮杂环卡宾和氮给体混合配体的钯络合物,即氮杂环卡宾-磺酰胺的Ⅱ-7,氮杂环卡宾-水杨醛亚胺的Ⅱ-14,氮杂环卡宾-苯甲醛亚胺的Ⅱ-18,以及氮杂环卡宾-胺基的Ⅱ-19。
它们的结构均通过NMR、MS和IR等表征,其中络合物Ⅱ-7、Ⅱ-14和Ⅱ-18的结构还经过X-Ray单晶衍射分析的确认。在金属钯周围,络合物Ⅱ-7、Ⅱ-14和Ⅱ-18均表现为三齿螯合的配位方式,而络合物Ⅱ-19则可能是由氮杂环卡宾与胺基两齿螯合在钯中心的结构。
3双齿双氮杂环卡宾的二价钯络合物在烯烃双氧化反应中的应用
以PhI(OAc)2作为促进PdⅡ/PdⅣ催化循环的氧化剂,在耐空气和水气的温和条件下,氮杂环卡宾的二价钯络合物能够成功地催化烯烃的双氧化反应,其中,阳离子的钯络合物Ⅰ-2d表现出最高的催化活性。对于1,2-双取代的烯烃底物,它们的双氧化反应能够取得良好的顺式非对映选择性；而对于苯乙烯类衍生物,则会得到其1,2-和1,l-双氧化的混合产物,其中,富电子的衍生物有利于1,1-双氧化产物的生成。
另外,通过同位素标记实验,我们还对该反应PdⅡ/PdⅣ催化循环的机理做了相应的研究,从而对各种产物的分配比例和非对映选择性做出了合理的解释。
4单齿氮杂环卡宾配体的金络合物的合成及其应用
从光学纯的联萘胺出发,合成了一系列单齿氮杂环卡宾配体的金络合物Ⅳ-1,Ⅳ-2a,b和Ⅳ-3-11,它们的结构经过了核磁、质谱和红外等的表征。其中,络合物Ⅳ-1,Ⅳ-2a和Ⅳ-6的结构还得到X-Ray单晶衍射分析的确认,它们的卡宾碳原子和阴离子配体在金的周围均表现为近似直线形的配位方式。
这些氮杂环卡宾的金络合物能够有效地催化联烯-醇Ⅳ-47的分子内环化反应,在室温下能以优秀的收率得到相应的醚产物,但是反应的手性诱导效果(up to 24% ee)却并不理想。
这些氮杂环卡宾的金络合物也能高效地催化1,6-烯炔的分子内环化反应,反应均能以很快的速率顺利进行。其中,络合物Ⅳ-6是最好的催化剂,在0°C下,以最高>99%的收率和59%ee的对映选择性得到相应的乙酰氧基环化产物Ⅳ-50a。
以Ph2SO作为氧化剂,氮杂环卡宾的金络合物还能高效地催化1,6-烯炔的氧化重排反应,这实际上是捕获到了金催化1,6-烯炔重排过程中的五元环并三元环的金卡宾中间体B。其中,络合物Ⅳ-2a是最好的催化剂,在10°C下,以最高达>99%的收率和65%ee的对映选择性得到相应的醛产物Ⅳ-53。
This thesis was mainly focused on the synthesis of N-heterocyclic carbene (NHC) ligands derived from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and their palladium(Ⅱ) and gold(Ⅰ) complexes, and applications of these complexes in the catalytic transformations.
1 Synthesis and application of bidentate bis(NHC)-Pd(Ⅱ) complexes
A series of axially chiral bis(NHC)-Pd(II) complexes I-la,b, I-2a-d, I-3a and I-4a-h bearing different coordinating counterions and N-substituents have been prepared from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and fully characterized by NMR, MS and IR spectroscopies et al.. The structure of complex I-4c was also confirmed by its single-crystal X-ray diffraction study.
These bis(NHC)-Pd(II) complexes as catalysts were effective in Et2Zn-mediated enantioselective umpolung allylation of aldehydes with cyclohexenyl acetate. While the variation of coordinating anion counterions may significantly change the raction rate, the enantioselectivity was both affected by coordinating counterions on palladium center and N-substituents around the N-heterocycle. For both aromatic and aliphatic aldehydes, complex I-4b bearing bromide counterions and N-CH2Ph substituents was the best catalyst to afford the homoallylic alcohol products in moderate to excellent yields (58%-96%), modest enantioselcetivities (54%-66% ee), and good to excellent syn diastereoselectivities (up to> 99:1 dr).
2 Synthesis and characterization of palladium(Ⅱ) complexes of chelating NHC-N donor hybrid ligands
A new class of palladium(Ⅱ) complexes of chelating NHC-N donor hybrid ligands such as NHC-sulfonamide (Ⅱ-7), NHC-phenoxyimine (Ⅱ-14), NHC-phenylimine (Ⅱ-18) and NHC-amine (Ⅱ-19) have been successfully synthesized in modest yields from optically pure 1,1'-binaphthyl-2,2'-diamine (BINAM).
These complexes have been characterized by all NMR, MS and IR spectroscopic data. The structures of II-7,11-14 and 11-18 were also confirmed by single-crystal X-ray diffraction studies to exhibit tridentate chelating motifs around the palladium center, but complexⅡ-19 was proposed to comprise a bidentate chelating NHC-amine hybrid ligand and two bromide counterions.
3 Bidentate bis(NHC)-palladium(II) complex-catalyzed dioxygenation of alkenes
Bis(NHC)-palladium(II) complex were successfully used to catalyze the dioxygenation of alkenes under mild conditions tolerant of air and moisture, by using PhI(OAc)2 as the oxidant for its PdⅡ/PdⅣcatalytic cycle. Cationic NHC-Pd2+ diaquo complexⅠ-2d exhibited the highest catalytic activity to give 1,2-dioxygenation products with good syn-diastereoselectivity for 1,2-disubstituted alkenes, but styrene derivatives often afforded both 1,2- and 1,1-dioxygenation products with electron-rich derivatives being more liable to form the 1,1-dioxygenation product.
By isotopic labeling experiments, we also investigated the possible mechanism involving PdⅡ/PdⅣcatalytic cycle to reasonably reveal the distribution of different products and their diastereoselectivities.
4 Synthesis and applications of monodentate NHC-Au(I) complexes
A series of axially chiral NHC-Au(I) complexesⅣ-1,Ⅳ-2a,b and IV-3-11 have been successfully synthesized from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) and fully characterized by NMR, MS and IR spectroscopies et al. The structures of complexesⅣ-1,Ⅳ-2a andⅣ-6 were also confirmed by single-crystal X-ray diffraction studies, exhibiting a nearly linear coordination geometry of NHC and anion counterion ligands around gold center.
These NHC-Au(I) complexes could effectively catalyze the intramolecular hydroalkoxylation of allenes to afford the ether product. in excellent yields but with unsatisfactory low enantioselectivities (up to 24% ee).
These NHC-Au(I) complexes as catalysts were successfully applied in the intramolecular cyclization of 1,6-enynes. ComplexⅣ-6 was examined to be the best catalyst giving the acetoxyl productⅣ-50a in up to>99% yield and 59% ee under 0℃condition.
The oxidative rearrangement of 1,6-enynes could also proceed smoothly with these NHC-Au(Ⅰ) complexes as catalysts by using Ph2SO as the oxidant, which is in fact the interception of cyclopropane gold(I)-carbenoid intermediate B for the gold(I)-catalyzed rearrangement of 1,6-enyne. ComplexⅣ-2a afforded the best results of up to>99% yield and 65% ee for the corresponding aldehyde productⅣ-53 under the condition of 10℃.
引文
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