Jacobsen催化剂的合成及其在不对称合成中的应用
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摘要
Salen金属催化剂特别是Jacobsen催化剂在催化不对称合成中应用十分广泛,如烃的不对称环氧化反应、外消旋环氧化合物的水解动力学拆分、Strecker反应、不对称氰硅烷化、消旋环氧化合物的不对称开环反应、Diels-Alder环加成反应、不对称环丙烷化反应等。
本论文主要由以下三部分组成:
(1) Jacobsen催化剂的合成。从消旋的环己二胺出发,通过酒石酸拆分分别得到(R,R)-1,2-环己二胺-(+)-酒石酸盐和(S,S)-1,2-环己二胺-(+)-酒石酸盐,然后与3,5-二叔丁基-2-羟基苯甲醛反应制得手性的Jacobsen催化剂,并通过紫外光谱、红外光谱、1H NMR、1C NMR等方法对其结构进行了表征。
(2)在上述基础上,对环氧氯丙烷进行水解动力学拆分,系统的研究了反应温度、时间、催化剂浓度、催化剂的循环使用次数等各种因素对产品的产率和光学纯度的影响,为以后的工业化生产提供了一个可靠的依据。
(3)丙酰左卡尼汀盐酸盐合成工艺的研究。以S-(+)-环氧氯丙烷为起始原料,经胺化、氰化、水解、酯化反应而得到丙酰左卡尼汀盐酸盐。其结构经过IR、MS、NMR以及元素分析确证。该工艺具有反应条件温和,易于操作,成本较低的优点。
Salen metal catalysts,especially Jacobsen catalyst,have been widely used in catalytic symmetric reaction, such as asymmetric epoxidizing reaction of Olefine, hydrolytic kinetic resolution of meso epoxides, Strecker reaction, asymmetric cyanide silane, asymmetric ring opening of racemic terminal epoxides, racemic epoxides open-loop asymmetric reactions, the Diels-Alder cycloaddition, asymmetric cyclopropanation, and so on.
This thesis consists of three parts:
(1) Synthesis of Jacobsen catalyst. (R,R)-1, 2-diammoniumcyclohexane mono-(+)- tartrate salt and (S,S)-1, 2-diammoniumcyclohexane mono-(+)-tartrate are acquired through the resolution of cis/trans-1, 2-diammoniumcyclohexane, and react with 3, 5- Di-tert- butyl-2- Hydroxybensaldehyde and get Jacobsen catalyst in the end. Their structures are characterized by UV, IR, 1H NMR, 13C NMR.
(2) Hydrolytic kinetic resolution of epihalohydrin. Systematic study of reaction temperature, time, concentrations of catalyst, and recycle times of catalyst on how to affect the yield and optical purity of production. This research can be provided a reliable basis for industrial production.
(3) Synthesis of PLC. PLC is synthesized by amination, cyanidation, hydrolytic action and esterification with S- epihalohydrin as starting material, and identified by IR, MS, NMR as well as element analysis. This process has the advantages of mild conditions, convenient operations, besides low cost.
本论文主要由以下三部分组成:
(1) Jacobsen催化剂的合成。从消旋的环己二胺出发,通过酒石酸拆分分别得到(R,R)-1,2-环己二胺-(+)-酒石酸盐和(S,S)-1,2-环己二胺-(+)-酒石酸盐,然后与3,5-二叔丁基-2-羟基苯甲醛反应制得手性的Jacobsen催化剂,并通过紫外光谱、红外光谱、1H NMR、1C NMR等方法对其结构进行了表征。
(2)在上述基础上,对环氧氯丙烷进行水解动力学拆分,系统的研究了反应温度、时间、催化剂浓度、催化剂的循环使用次数等各种因素对产品的产率和光学纯度的影响,为以后的工业化生产提供了一个可靠的依据。
(3)丙酰左卡尼汀盐酸盐合成工艺的研究。以S-(+)-环氧氯丙烷为起始原料,经胺化、氰化、水解、酯化反应而得到丙酰左卡尼汀盐酸盐。其结构经过IR、MS、NMR以及元素分析确证。该工艺具有反应条件温和,易于操作,成本较低的优点。
Salen metal catalysts,especially Jacobsen catalyst,have been widely used in catalytic symmetric reaction, such as asymmetric epoxidizing reaction of Olefine, hydrolytic kinetic resolution of meso epoxides, Strecker reaction, asymmetric cyanide silane, asymmetric ring opening of racemic terminal epoxides, racemic epoxides open-loop asymmetric reactions, the Diels-Alder cycloaddition, asymmetric cyclopropanation, and so on.
This thesis consists of three parts:
(1) Synthesis of Jacobsen catalyst. (R,R)-1, 2-diammoniumcyclohexane mono-(+)- tartrate salt and (S,S)-1, 2-diammoniumcyclohexane mono-(+)-tartrate are acquired through the resolution of cis/trans-1, 2-diammoniumcyclohexane, and react with 3, 5- Di-tert- butyl-2- Hydroxybensaldehyde and get Jacobsen catalyst in the end. Their structures are characterized by UV, IR, 1H NMR, 13C NMR.
(2) Hydrolytic kinetic resolution of epihalohydrin. Systematic study of reaction temperature, time, concentrations of catalyst, and recycle times of catalyst on how to affect the yield and optical purity of production. This research can be provided a reliable basis for industrial production.
(3) Synthesis of PLC. PLC is synthesized by amination, cyanidation, hydrolytic action and esterification with S- epihalohydrin as starting material, and identified by IR, MS, NMR as well as element analysis. This process has the advantages of mild conditions, convenient operations, besides low cost.
引文
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[7] Sigman M S, Jacobsen E N. Enantioselective Addition of Hydrogen Cyanide to Imines Catalyzed by a Chiral (Salen)Al(III) Complex[J]. J. Am. Chem. Soc., 1998, 120(21): 5315-5316.
[8] Belokon' Y N , Caveda C S, Green B. et al. The Asymmetric Addition of Trimethylsilyl Cyanide to Aldehydes Catalyzed by Chiral (Salen)TitaniumComplexes[J]. J. Am. Chem. Soc., 1999, 121(16): 3968-3973.
[9] SchausS E, Larrow J F, Jacobsen E N. Practical Synthesis of Enantiopure Cyclic 1,2-Amino Alcohols via Catalytic Asymmetric Ring Opening of Meso Epoxides[J]. J. Org. Chem., 1997, 62(12): 4197-4199.
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[17] Kosior M, Kwiatkowski P, Jurczak J. Stereochemistry of the Diels–Alder reaction at high pressure: diastereo- and enantioselective [4+2] cycloaddition of buta-1,3-dieneto glyoxylic acid derivatives catalysed by (salen) chromium(III) complexes[J]. Tetrahedron: Asymmetry., 2005, 16: 2897-2900.
[18] Hinterding K, Jacobsen E N. Regioselective Carbomethoxylation of Chiral Epoxides: A New Route to Enantiomerically Pureβ-Hydroxy Esters[J]. J. Org. Chem., 1999, 64: 2164-2165.
[19] Tokunage M, Larrow J F, Jacobsen E N. et al. Asymmetric catalysis with water: efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis[J]. Science., 1997, 277: 936-938.
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[21] Brandes B D, Jacobsen E N. Synthesis of enantiopure 3-chlorostyrene oxide via an asymmetric epoxidation-hydrolytic kinetic resolution sequence[J] . Tetrahedron: Asymmetry.,1997, 8, 3927-3933.
[22] Leighton J L, Jacobsen E N. Efficient Synthesis of (R)-4-((Trimethylsilyl)oxy) -2- cyclopentenone by Enantioselective Catalytic Epoxide Ring Opening[J]. J. Org. Chem., 1996, 61(1): 389-390.
[23] Jacobsen E N. Asymmetric Catalysis of Epoxide Ring-Opening Reactions[J]. Acc. Chem. Res., 2000, 33(6): 421-431.
[24] Bartoli G, Bosco M, Carlone A. et al. Asymmetric Aminolysis of Aromatic Epoxides: A Facile Catalytic Enantioselective Synthesis of anti-β-Amino Alcohols[J]. Org. Lett., 2004, 6 (13): 2173-2176.
[25] [Bartoli G, Bosco M, Carlone A. et al. Asymmetric Catalytic Synthesis of Enantiopure N-Protected 1,2-Amino Alcohols[J]. Org. Lett., 2004, 6 (22): 3973-3975.
[26] Sigman M S, Jacobsen E N. Enantioselective Addition of Hydrogen Cyanide to Imines Catalyzed by a Chiral (Salen)Al(III) Complex[J]. J. Am. Chem. Soc., 1998, 120(21): 5315-5316
[27] Larrow J F, Schaus S E, Jacobsen E N. Kinetic Resolution of Terminal Epoxides viaHighly Regioselective and Enantioselective Ring Opening with TMSN3. An Efficient, Catalytic Route to 1,2-Amino Alcohols[J]. J. Am. Chem. Soc., 1996, 118: 7420-7421.
[28] Schaus S E, Brandes B D, Larrow J F. et al. Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral (salen)CoIII Complexes. Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols[J]. J. Am. Chem. Soc., 2002, 124(7): 1307-1315.
[29] White D E, Jacobsen E N. New oligomeric catalyst for the hydrolytic kinetic resolution of terminal epoxides under solvent-free conditions[J]. Tetrahedron: Asymmetry., 2003, 14: 3633-3638.
[30] Song Y M, Chen H L, Zhuo Z. Highly enantioselective resolution of terminal epoxides with cross-linked polymeric Salen-Co(III) complexes[J]. Tetrahedron letters., 2003, 44: 7081-7085.
[31] Shin C K, Kim S J, Kim G L. New chiral cobalt salen complexes containing Lewis acid BF3; a highly reactive and enantioselective catalyst for the hydrolytic kinetic resolution of epoxides[J]. Tetrahed. Lett., 2004, 45: 7429-7433.
[32] Hansen K B, Leighton J L, Jacobsen E N. On the Mechanism of Asymmetric Nucleophilic Ring-Opening of Epoxides Catalyzed by (Salen)CrIII Complexes[J]. J. Am. Chem. Soc., 1996, 118(44): 10924-10925.
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[2] Wierenga W, Harrison , Evans B R. et al . Antibacterial benzisoxazolones. An unusual rearrangement product from o-nitrostyrene oxide en route to the photolabile carbonyl protecting group, (o-nitrophenyl)ethylene glycol[J]. J. Org. Chem., 1984, 49(3): 438-442.
[3] Moreau S P, Morisseau C, Baratti J. et al. Microbiological transformations 37. An enantioconvergent synthesis of theβ-blocker (R)-Nifénalol? using a combined chemoenzymatic approach [J]. Tetrahedron, 1997, 53: 9707-9714.
[4] Brandes B D, Jacobsen E N. Synthesis of enantiopure 3-chlorostyrene oxide via an asymmetric epoxidation-hydrolytic kinetic resolution sequence [J]. Tetrahedron: Asymmetry., 1997, 8: 3927-3933.
[5] Finney N S, Pospisil P J, Jacobsen E N. et al. On the Viability of Oxametallacyclic Intermediates in the (salen)Mn-Catalyzed Asymmetric Epoxidation[J]. Angew. Chem. Int. Ed. Engl., 1997, 36: 1720.
[6] Tokunage M, Larrow J F, Jacobsen E N. Asymmetric Catalysis with Water: Efficient Kinetic Resolution of Terminal Epoxides by Means of Catalytic Hydrolysis[J]. Science, 1997, 277: 936-938.
[7] Sigman M S, Jacobsen E N. Enantioselective Addition of Hydrogen Cyanide to Imines Catalyzed by a Chiral (Salen)Al(III) Complex[J]. J. Am. Chem. Soc., 1998, 120(21): 5315-5316.
[8] Belokon' Y N , Caveda C S, Green B. et al. The Asymmetric Addition of Trimethylsilyl Cyanide to Aldehydes Catalyzed by Chiral (Salen)TitaniumComplexes[J]. J. Am. Chem. Soc., 1999, 121(16): 3968-3973.
[9] SchausS E, Larrow J F, Jacobsen E N. Practical Synthesis of Enantiopure Cyclic 1,2-Amino Alcohols via Catalytic Asymmetric Ring Opening of Meso Epoxides[J]. J. Org. Chem., 1997, 62(12): 4197-4199.
[10] White D E, Jacobsen E N. New oligomeric catalyst for the hydrolytic kinetic resolution of terminal epoxides under solvent-free conditions[J]. Tetrahedron: Aymmetry., 2003, (14): 3633-3638.
[11] Schaus S E, Branalt J, Jacobsen E N. Asymmetric Hetero-Diels-Alder Reactions Catalyzed by Chiral (Salen)Chromium(III) Complexes[J]. J. Org. Chem., 1998, 63(2): 403-405.
[12] Akira Nakamura, Akira Konishi, Yoshitaka Tatsuno, et al. A highly enantioselective synthesis of cyclopropane derivatives through chiral cobalt(II) complex catalyzed carbenoid reaction. General scope and factors determining the enantioselectivity[J]. J. Am. Chem. Soc., 1978, 100(11): 3443-3448.
[13] Yao X Q, Chen H L, Lu W R. et al. Enantioselective epoxidation of olefins catalyzed by two novel chiral poly-salen–Mn(III) complexes[J]. Tetrahedron Lett., 2000, 41: 10267-10271.
[14] Jacobsen E N, Kakiuchi F, Konsler R G. et al. Enantioselective Catalytic Ring Opening of Epoxides with Carboxylic Acids[J]. Tetrahedron Lett., 1997, 38(5): 773-776.
[15] Effenberger F. Synthesis and Reactions of Optically Active Cyanohydrins[J]. Angew. Chem. Int. Ed. Engl., 1994, 33: 1555.
[16] Li L S, Wu Y K, Wu Y L, et al. Asymmetric hetero-Diels--Alder reaction of 1-alkyl-3-silyloxy-1,3-dienes with ethyl glyoxylate catalyzed by a chiral (salen)cobalt(II) complex[J]. Tetrahedron: Asymmetry., 1998, 9 (13): 2271-2277.
[17] Kosior M, Kwiatkowski P, Jurczak J. Stereochemistry of the Diels–Alder reaction at high pressure: diastereo- and enantioselective [4+2] cycloaddition of buta-1,3-dieneto glyoxylic acid derivatives catalysed by (salen) chromium(III) complexes[J]. Tetrahedron: Asymmetry., 2005, 16: 2897-2900.
[18] Hinterding K, Jacobsen E N. Regioselective Carbomethoxylation of Chiral Epoxides: A New Route to Enantiomerically Pureβ-Hydroxy Esters[J]. J. Org. Chem., 1999, 64: 2164-2165.
[19] Tokunage M, Larrow J F, Jacobsen E N. et al. Asymmetric catalysis with water: efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis[J]. Science., 1997, 277: 936-938.
[20]李明,张雅文. Salen-Co(III)手性催化剂的合成与外消旋环氧化合物的水解动力学拆分[J].江南大学学报, 2002, 1(4): 361-364.
[21] Brandes B D, Jacobsen E N. Synthesis of enantiopure 3-chlorostyrene oxide via an asymmetric epoxidation-hydrolytic kinetic resolution sequence[J] . Tetrahedron: Asymmetry.,1997, 8, 3927-3933.
[22] Leighton J L, Jacobsen E N. Efficient Synthesis of (R)-4-((Trimethylsilyl)oxy) -2- cyclopentenone by Enantioselective Catalytic Epoxide Ring Opening[J]. J. Org. Chem., 1996, 61(1): 389-390.
[23] Jacobsen E N. Asymmetric Catalysis of Epoxide Ring-Opening Reactions[J]. Acc. Chem. Res., 2000, 33(6): 421-431.
[24] Bartoli G, Bosco M, Carlone A. et al. Asymmetric Aminolysis of Aromatic Epoxides: A Facile Catalytic Enantioselective Synthesis of anti-β-Amino Alcohols[J]. Org. Lett., 2004, 6 (13): 2173-2176.
[25] [Bartoli G, Bosco M, Carlone A. et al. Asymmetric Catalytic Synthesis of Enantiopure N-Protected 1,2-Amino Alcohols[J]. Org. Lett., 2004, 6 (22): 3973-3975.
[26] Sigman M S, Jacobsen E N. Enantioselective Addition of Hydrogen Cyanide to Imines Catalyzed by a Chiral (Salen)Al(III) Complex[J]. J. Am. Chem. Soc., 1998, 120(21): 5315-5316
[27] Larrow J F, Schaus S E, Jacobsen E N. Kinetic Resolution of Terminal Epoxides viaHighly Regioselective and Enantioselective Ring Opening with TMSN3. An Efficient, Catalytic Route to 1,2-Amino Alcohols[J]. J. Am. Chem. Soc., 1996, 118: 7420-7421.
[28] Schaus S E, Brandes B D, Larrow J F. et al. Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral (salen)CoIII Complexes. Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols[J]. J. Am. Chem. Soc., 2002, 124(7): 1307-1315.
[29] White D E, Jacobsen E N. New oligomeric catalyst for the hydrolytic kinetic resolution of terminal epoxides under solvent-free conditions[J]. Tetrahedron: Asymmetry., 2003, 14: 3633-3638.
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