金鸡纳生物碱衍生的亚磷酸酯配体的合成及其催化性能研究
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摘要
亚磷酸酯化合物是一种非常重要的手性膦配体,它们原料易得,合成简便,性质稳定,使用方便且易于进行电性和空间结构调节,因此倍受人们青睐。
金鸡纳生物碱是一类来源广泛的手性天然产物,它们所具有的结构特征,使之成为理想的手性配体骨架,金鸡纳碱结构中C9-OH很容易修饰为亚磷酸酯。我们以金鸡纳生物碱和手性二醇为原料合成了系列金鸡纳生物碱衍生的亚磷酸酯配体,并将它们用于催化不对称烯丙基烷基化反应。此外,还将所合成的亚磷酸酯化合物作为有机催化剂,考察其在去对称反应中的催化性能。
光学纯的环氧化物是一类重要的有机合成中间体,而手性胺盐有机催化剂催化的α,β-不饱和酮的不对称环氧化反应是合成手性环氧化合物最直接和最简便的途径。
本论文以金属配合物催化剂和有机催化剂催化不对称反应为切入点,主要完成了以下工作:
1、以辛可宁、辛可尼丁、奎宁、奎尼丁、二氢奎宁和二氢奎尼丁等为原料,合成了4类(10种)金鸡纳生物碱衍生的亚磷酸酯配体,并用1H NMR、13C NMR、31P NMR和MS进行了结构表征。
2、将上述10种亚磷酸酯配体和[Pd(η3-C3H5)Cl]2配位生成金属配合物催化剂,用于催化1,3-二苯基烯丙基醋酸酯和丙二酸二甲酯的不对称烯丙基烷基化反应,实验结果表明:
(1) L1-CN生成的催化剂催化的烯丙基烷基化反应,催化效果最好,化学产率可达100%,光学产率可达94%ee;
(2) L1-CN和L1-QND的钯配合物催化剂比L1-CND和L1-QN钯配合物催化剂的催化活性高,即C8、C9位构型为(8R, 9S)的金鸡纳生物碱衍生的催化剂催化效果优于C8、C9位构型为(8R, 9S)金鸡纳生物碱衍生的催化剂;
(3)构型不同的手性1,2-二苯基-1,2-乙二醇生成的亚磷酸酯配体,其钯配合物催化烯丙基烷基化反应生成的产物构型不同;
(4)溶剂对催化反应影响较大,以L1-CN衍生的配合物催化剂催化反应,于室温下在CH2Cl2中化学产率可达100%,在甲苯、THF或乙腈中化学产率较低,在DMF中根本不反应;
(5)在L1-CN-钯配合物催化的反应中,加入醋酸盐添加剂,对化学产率影响不大,但会影响立体选择性。
3、考察亲核试剂种类、反应温度对配体L1-CN、L1-CND、L1-QN和L1-QND生成的催化剂催化1,3-二苯基烯丙基醋酸酯的不对称烯丙基烷基化反应的影响,实验结果表明:
(1)亲核试剂种类对反应活性有较大影响。乙酰基丙酮和3-甲基-2,4-戊二酮作为亲核试剂比丙二酸二甲酯的反应活性高;
(2)反应温度对这四种配体诱导的不对称催化反应的活性和立体选择性有较大影响。降低反应温度,化学产率随之降低,但光学产率有所提高,在-40℃时光学产率均在90%ee以上。
4、L1-CN配体和过渡金属Rh和Ir配位生成的催化剂,在不对称催化氢化和不对称氢转移反应中的催化活性不尽人意。
5.以L1-CN、L2、L3和L4四种亚磷酸酯化合物作为有机催化剂,催化meso-1,2-二苯基-1,2-乙二醇的去对称反应,最高以42%的产率获得53%ee的产物。
6.合成了3种金鸡纳生物碱衍生的手性胺A6、A7和A8,首次考察了它们和其它5种手性胺A1~A5形成的铵盐在链状α,β-不饱和酮的不对称环氧化反应中的催化效果,实验结果表明:
(1)以查尔酮为底物、TBHP为氧化剂进行的不对称环氧化反应,手性胺A6的催化效果最好,光学产率可达74.8%ee;
(2)考察了几种氧化剂对查尔酮的不对称环氧化反应的影响,其中TBHP作为氧化剂,反应的催化活性和立体选择性最高;
(3)溶剂对不对称环氧化反应立体选择性影响甚微,但化学活性有差别,在正己烷中进行的催化反应活性最高,化学产率为75%;
(4)首次考察了β-环糊精修饰的手性二胺衍生的催化剂催化查尔酮的不对称环氧化反应,以33%产率得到24.8%ee的环氧化物。
(5)将A6形成的铵盐用于催化其它7种α,β-不饱和酮的不对称环氧化反应,考察了α,β-不饱和酮的结构及电性因素对反应效果的影响,其中1-苯基3-对甲氧基苯基-2-丙烯酮是最适合的底物。
In recent years, phosphites have emerged as suitable ligands for many metal -catalyzed asymmetric processes. Due to their easy preparation from readily available alcohols, phosphites ligands are extremely attractive for catalysis. Simultaneously, the availability of many alcohols makes simple ligand-tuning possible, which allows the synthesis of many series of chiral ligands screened for high activity and selectivity. In addition, phosphites are less sensitive to oxidation than phosphines, which also makes their application more convenient.
The Cinchona alkaloids quinine, quindine, cinchonidine and cinchonine are extracted from the bark of the cinchona tree and can be produced on a commercial scale. Because of their special structure, they can be employed as“privileged”ligands backbone. The hydroxyl group at C9 in Cinchona alkaloid structure could be readily modified to give phosphites. So in our work, a novel family of phosphites was designed and synthesized from Cinchona alkaloids and enantiopure diol. The application of these new phosphites to palladium-catalyzed asymmetric allylic alkylation (AAA) of 1,3-diphenyl-2-propenyl acetate was also investigated. Furthermore, their organocatalytic ability in asymmetric desymme -trization of meso-hydrobenzoin was also examined.
Catalytic asymmetric epoxidation (AE) holds a prominent place in asymmetric catalysis due to the fundamental importance of epoxides in organic chemistry. The AE reaction ofα,β-enones activated by chiral amine salts, a kind of organocatalyst, makes the preparation of chiral epoxides more simple and convenient. So some chiral diamine as organocatalyst in AE reaction ofα,β-enones were tested in our experiments.
The work focuses on the reaction catalyzed by transitional-metal-ligands complexes and organocatalysts. It covers the following 5 aspects:
1. Ten novel phosphites were synthesized from cinchonine, cinchonodine, quinine, quinidine, dihydroquinine and dihydroquindine with the yields ranged from 56% to 75%. Their structures were also confirmed by 1H NMR, 13C NMR, 31P NMR and MS.
2. With the target ten ligands in hand, attention was turned to investigate their potential utilities in AAA reaction of 1,3-diphenyl-2-propenyl acetate with the dimethyl malonate as nucleophile. The results can be summarized as follows:
(1) The best results were obtained by L1-CN with the chemical yields up to 100% and the enantioselectivities up to 94%ee.
(2) Cinchonine and quindine-derived ligands L1-CN, L1-QND exhibited better catalytic activity and stereoselectivity than their pseudo-enantiomers L1-CND, L1-QN did. The configuration of C8, C9 have effect on the catalytic ability.
(3) Not the structure backbone of cinchona alkaloid in ligands but that of enantiopure 1,2-diphenyl-1,2-ethanediol was responsible for the configurations of products.
(4) The solvent was found to influence the reaction activity greatly when L1-CN was used in AAA reaction. No expected product was obtained in DMF with only lesser one in toluene, THF and CH3CN. CH2Cl2 was proved to be the proper solvent for AAA reaction.
(5) In AAA reaction catalyzed by L1-CN-Pd complex, the base additives only influenced the asymmetric induction to some extent. The addition of KOAc could improve the enantioselectivity of AAA reaction.
3. The effect of nucleophiles and temperature on AAA reaction was also probed.
The conclusions were drawn as follows:
(1) The reaction, with acetylacetone rather than dimethyl malonate as nucleophile gave the corresponding products with high yields. Similar improvement was also found in the same reaction when 3-methyl-2,4 -pentanedione was employed as nucleophile.
(2) The dependence of temperature in the AAA reaction was also found. Like most of asymmetric catalysis reactions, the substrates conversion decreased and the enantioselectivity was improved when temperature was lowered. At -40℃, the best stereoselectivity was obtained.
4. L1-CN ligand was also assessed in Rh and Ir-catalyzed asymmetric transfer hydrogenation and asymmetric hydrogenation. However, both failed.
5. Phosphites L1-CN, L2, L3 and L4 were applied in organocatalytic aymmetric desymmerization of meso-hydrobenzoin. L4 gave the best result with 42% yield and 53%ee.
6. Three kinds of cinchona alkaloids derivatives A6, A7, A8 were synthesized and applied in the amine-catalyzed AE reaction ofα,β-unsaturated enones. The catalytic activities and enantioselectivities of other amines A1~A5 in the reactions were also examined. The results were summarized as follows:
(1) In the AE reactions of chalcone, A6 was found to give a better enantiomeric excess (74.8%ee) than other seven chiral amines.
(2) The influence of oxidants on the reaction activity and enantioselectivity was observed. TBHP was proved to be the most suitable in amine-catalyzed AE reaction of chalcone. Simultaneously, reactions carried out in different solvents produced similar optical yields though only n-hexane can give the best chemical yield (75%).
(3)β-CD-derived diamine A5 also showed a little asymmetric induction(33% yield, 24.8%ee). It’s the first example thatβ-CD-derived diamine be employed as organocatalyst in AE reaction.
(4) Several chalcone derivatives were converted to the corresponding optically active epoxides in the presence of A6. But the results showed that enones with para electron-donating substituents in theβ-phenyl group can produce better enantioselectivities.
金鸡纳生物碱是一类来源广泛的手性天然产物,它们所具有的结构特征,使之成为理想的手性配体骨架,金鸡纳碱结构中C9-OH很容易修饰为亚磷酸酯。我们以金鸡纳生物碱和手性二醇为原料合成了系列金鸡纳生物碱衍生的亚磷酸酯配体,并将它们用于催化不对称烯丙基烷基化反应。此外,还将所合成的亚磷酸酯化合物作为有机催化剂,考察其在去对称反应中的催化性能。
光学纯的环氧化物是一类重要的有机合成中间体,而手性胺盐有机催化剂催化的α,β-不饱和酮的不对称环氧化反应是合成手性环氧化合物最直接和最简便的途径。
本论文以金属配合物催化剂和有机催化剂催化不对称反应为切入点,主要完成了以下工作:
1、以辛可宁、辛可尼丁、奎宁、奎尼丁、二氢奎宁和二氢奎尼丁等为原料,合成了4类(10种)金鸡纳生物碱衍生的亚磷酸酯配体,并用1H NMR、13C NMR、31P NMR和MS进行了结构表征。
2、将上述10种亚磷酸酯配体和[Pd(η3-C3H5)Cl]2配位生成金属配合物催化剂,用于催化1,3-二苯基烯丙基醋酸酯和丙二酸二甲酯的不对称烯丙基烷基化反应,实验结果表明:
(1) L1-CN生成的催化剂催化的烯丙基烷基化反应,催化效果最好,化学产率可达100%,光学产率可达94%ee;
(2) L1-CN和L1-QND的钯配合物催化剂比L1-CND和L1-QN钯配合物催化剂的催化活性高,即C8、C9位构型为(8R, 9S)的金鸡纳生物碱衍生的催化剂催化效果优于C8、C9位构型为(8R, 9S)金鸡纳生物碱衍生的催化剂;
(3)构型不同的手性1,2-二苯基-1,2-乙二醇生成的亚磷酸酯配体,其钯配合物催化烯丙基烷基化反应生成的产物构型不同;
(4)溶剂对催化反应影响较大,以L1-CN衍生的配合物催化剂催化反应,于室温下在CH2Cl2中化学产率可达100%,在甲苯、THF或乙腈中化学产率较低,在DMF中根本不反应;
(5)在L1-CN-钯配合物催化的反应中,加入醋酸盐添加剂,对化学产率影响不大,但会影响立体选择性。
3、考察亲核试剂种类、反应温度对配体L1-CN、L1-CND、L1-QN和L1-QND生成的催化剂催化1,3-二苯基烯丙基醋酸酯的不对称烯丙基烷基化反应的影响,实验结果表明:
(1)亲核试剂种类对反应活性有较大影响。乙酰基丙酮和3-甲基-2,4-戊二酮作为亲核试剂比丙二酸二甲酯的反应活性高;
(2)反应温度对这四种配体诱导的不对称催化反应的活性和立体选择性有较大影响。降低反应温度,化学产率随之降低,但光学产率有所提高,在-40℃时光学产率均在90%ee以上。
4、L1-CN配体和过渡金属Rh和Ir配位生成的催化剂,在不对称催化氢化和不对称氢转移反应中的催化活性不尽人意。
5.以L1-CN、L2、L3和L4四种亚磷酸酯化合物作为有机催化剂,催化meso-1,2-二苯基-1,2-乙二醇的去对称反应,最高以42%的产率获得53%ee的产物。
6.合成了3种金鸡纳生物碱衍生的手性胺A6、A7和A8,首次考察了它们和其它5种手性胺A1~A5形成的铵盐在链状α,β-不饱和酮的不对称环氧化反应中的催化效果,实验结果表明:
(1)以查尔酮为底物、TBHP为氧化剂进行的不对称环氧化反应,手性胺A6的催化效果最好,光学产率可达74.8%ee;
(2)考察了几种氧化剂对查尔酮的不对称环氧化反应的影响,其中TBHP作为氧化剂,反应的催化活性和立体选择性最高;
(3)溶剂对不对称环氧化反应立体选择性影响甚微,但化学活性有差别,在正己烷中进行的催化反应活性最高,化学产率为75%;
(4)首次考察了β-环糊精修饰的手性二胺衍生的催化剂催化查尔酮的不对称环氧化反应,以33%产率得到24.8%ee的环氧化物。
(5)将A6形成的铵盐用于催化其它7种α,β-不饱和酮的不对称环氧化反应,考察了α,β-不饱和酮的结构及电性因素对反应效果的影响,其中1-苯基3-对甲氧基苯基-2-丙烯酮是最适合的底物。
In recent years, phosphites have emerged as suitable ligands for many metal -catalyzed asymmetric processes. Due to their easy preparation from readily available alcohols, phosphites ligands are extremely attractive for catalysis. Simultaneously, the availability of many alcohols makes simple ligand-tuning possible, which allows the synthesis of many series of chiral ligands screened for high activity and selectivity. In addition, phosphites are less sensitive to oxidation than phosphines, which also makes their application more convenient.
The Cinchona alkaloids quinine, quindine, cinchonidine and cinchonine are extracted from the bark of the cinchona tree and can be produced on a commercial scale. Because of their special structure, they can be employed as“privileged”ligands backbone. The hydroxyl group at C9 in Cinchona alkaloid structure could be readily modified to give phosphites. So in our work, a novel family of phosphites was designed and synthesized from Cinchona alkaloids and enantiopure diol. The application of these new phosphites to palladium-catalyzed asymmetric allylic alkylation (AAA) of 1,3-diphenyl-2-propenyl acetate was also investigated. Furthermore, their organocatalytic ability in asymmetric desymme -trization of meso-hydrobenzoin was also examined.
Catalytic asymmetric epoxidation (AE) holds a prominent place in asymmetric catalysis due to the fundamental importance of epoxides in organic chemistry. The AE reaction ofα,β-enones activated by chiral amine salts, a kind of organocatalyst, makes the preparation of chiral epoxides more simple and convenient. So some chiral diamine as organocatalyst in AE reaction ofα,β-enones were tested in our experiments.
The work focuses on the reaction catalyzed by transitional-metal-ligands complexes and organocatalysts. It covers the following 5 aspects:
1. Ten novel phosphites were synthesized from cinchonine, cinchonodine, quinine, quinidine, dihydroquinine and dihydroquindine with the yields ranged from 56% to 75%. Their structures were also confirmed by 1H NMR, 13C NMR, 31P NMR and MS.
2. With the target ten ligands in hand, attention was turned to investigate their potential utilities in AAA reaction of 1,3-diphenyl-2-propenyl acetate with the dimethyl malonate as nucleophile. The results can be summarized as follows:
(1) The best results were obtained by L1-CN with the chemical yields up to 100% and the enantioselectivities up to 94%ee.
(2) Cinchonine and quindine-derived ligands L1-CN, L1-QND exhibited better catalytic activity and stereoselectivity than their pseudo-enantiomers L1-CND, L1-QN did. The configuration of C8, C9 have effect on the catalytic ability.
(3) Not the structure backbone of cinchona alkaloid in ligands but that of enantiopure 1,2-diphenyl-1,2-ethanediol was responsible for the configurations of products.
(4) The solvent was found to influence the reaction activity greatly when L1-CN was used in AAA reaction. No expected product was obtained in DMF with only lesser one in toluene, THF and CH3CN. CH2Cl2 was proved to be the proper solvent for AAA reaction.
(5) In AAA reaction catalyzed by L1-CN-Pd complex, the base additives only influenced the asymmetric induction to some extent. The addition of KOAc could improve the enantioselectivity of AAA reaction.
3. The effect of nucleophiles and temperature on AAA reaction was also probed.
The conclusions were drawn as follows:
(1) The reaction, with acetylacetone rather than dimethyl malonate as nucleophile gave the corresponding products with high yields. Similar improvement was also found in the same reaction when 3-methyl-2,4 -pentanedione was employed as nucleophile.
(2) The dependence of temperature in the AAA reaction was also found. Like most of asymmetric catalysis reactions, the substrates conversion decreased and the enantioselectivity was improved when temperature was lowered. At -40℃, the best stereoselectivity was obtained.
4. L1-CN ligand was also assessed in Rh and Ir-catalyzed asymmetric transfer hydrogenation and asymmetric hydrogenation. However, both failed.
5. Phosphites L1-CN, L2, L3 and L4 were applied in organocatalytic aymmetric desymmerization of meso-hydrobenzoin. L4 gave the best result with 42% yield and 53%ee.
6. Three kinds of cinchona alkaloids derivatives A6, A7, A8 were synthesized and applied in the amine-catalyzed AE reaction ofα,β-unsaturated enones. The catalytic activities and enantioselectivities of other amines A1~A5 in the reactions were also examined. The results were summarized as follows:
(1) In the AE reactions of chalcone, A6 was found to give a better enantiomeric excess (74.8%ee) than other seven chiral amines.
(2) The influence of oxidants on the reaction activity and enantioselectivity was observed. TBHP was proved to be the most suitable in amine-catalyzed AE reaction of chalcone. Simultaneously, reactions carried out in different solvents produced similar optical yields though only n-hexane can give the best chemical yield (75%).
(3)β-CD-derived diamine A5 also showed a little asymmetric induction(33% yield, 24.8%ee). It’s the first example thatβ-CD-derived diamine be employed as organocatalyst in AE reaction.
(4) Several chalcone derivatives were converted to the corresponding optically active epoxides in the presence of A6. But the results showed that enones with para electron-donating substituents in theβ-phenyl group can produce better enantioselectivities.
引文
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