(Z)-2-acetamidocinnamic acid methyl ester

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (Z)-2-acetamidocinnamic acid methyl ester
• 英文别名: methyl (Z)-2-acetamidocinnamate；methyl cis-2-acetamidocinnamate；methyl (Z)-acetamidocinnamate；methyl (Z)-3-(2-acetamidophenyl)prop-2-enoate
• 化学式: C₁₂H₁₃NO₃
• 分子量: 219.24
• InChiKey: OJRHLZXQEXLUGU-FPLPWBNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-2-acetamidocinnamic acid methyl ester 、 甲烷 、 (1S,5S,6S)-1,6-Bis(diphenylphosphinoxy)spiro[4,4]nonane 在 氢气 作用下， 以 甲醇 为溶剂， 以97%的产率得到N-乙酰-L-苯丙氨酸甲酯
  参考文献：
  名称：

  Chiral phosphinites

  摘要：

  已合成新的光学活性膦酸酯化合物，可用于不对称催化，并已用于制备铑催化剂。这种催化剂在对映选择性催化氢化反应中特别有用。

  公开号：

  US05756799A1

文献信息

• Chiral phosphinites
  申请人：The Hong Kong Polytechnic University

  公开号：US05756799A1

  公开（公告）日：1998-05-26

  New optically active phosphinite compounds which are useful in asymmetric catalysis have been synthesized and have been used in the preparation of rhodium catalysts. Such catalysts are particularly useful in enantioselective catalytic hydrogenation reactions.

  已合成新的光学活性膦酸酯化合物，可用于不对称催化，并已用于制备铑催化剂。这种催化剂在对映选择性催化氢化反应中特别有用。
• Process for the preparation of enantiomers of alpha-amino acid derivatives by asymmetric hydrogenation
  申请人：DSM N.V.

  公开号：EP0498507A1

  公开（公告）日：1992-08-12

  The inventor relates to a process for the preparation of (S)- and (R)-α-amino acid dervatives by asymmetric hydrogenation starting from a substrate of the formula I in which R¹denotes hydrogen or an alkyl group R²denotes a protecting group and R³denotes hydrogen, an alkyl, aryl, aralkyl, alkaryl, heteroalkyl or heteroaryl group, which is hydrogenated in the presence of a rhodium(I)complex catalyst of the formula II         /Rh(Z)(Lk)/⁺A⁻   II in which Rhdenotes rhodium Zdenotes a chiral chelating ligand with two trivalent phosphorous atoms as coordination partners for a bond to rhodium Ldenotes a solvent molecule kdenotes 0, 1, 2, or 3 and A⁻denotes an anion of a weakly coordinating acid, such as BF₄⁻, ClO₄⁻, SO₄H⁻, PF₆⁻, R⁴-COO⁻, or R⁴SO₃⁻, where R⁴ denotes a fluorinated alkyl or aryl group into an α-amino acid derivative of the formula III in which R¹denotes hydrogen or an alkyl group R²denotes a protecting group and R³denotes hydrogen, an alkyl, aryl, aralkyl, alkaryl, heteroalkyl or heteroaryl group in which process an amphiphilic substance of the formula IV         A-E   IV in which Adenotes a nonpolar alkyl chain with 5 to 20 carbon atoms or a glycerol dialkylether group and Edenotes a polar (hydrophilic)group, such as -O-SO₃Na, -SO₃Na, -O(CH₂CH₂O)nH or -OP⊖O₂/OCH₂CH₂N⊕(CH₃)₃/, where n is a number between 3 and 15. The hydrogenation can be carried out in a polar or nonpolar solvent.

  该发明涉及一种通过不对称氢化从具有以下结构的底物开始制备(S)-和(R)-α-氨基酸衍生物的过程，在该结构中R¹代表氢或烷基基团，R²代表保护基团，R³代表氢、烷基、芳基、芳基烷基、烷基芳基、杂原子烷基或杂原子芳基基团，该底物在存在Rhodium(I)配合物催化剂的情况下进行氢化，该配合物的结构如下： /Rh(Z)(Lk)/⁺A⁻   II 其中Rh代表铑，Z代表带有两个三价磷原子作为铑配位伙伴的手性螯合配体，L代表溶剂分子，k代表0、1、2或3，A⁻代表弱配位酸的阴离子，例如BF₄⁻、ClO₄⁻、SO₄H⁻、PF₆⁻、R⁴-COO⁻或R⁴SO₃⁻，其中R⁴代表氟化烷基或芳基基团，将其转化为具有以下结构的α-氨基酸衍生物： R¹代表氢或烷基基团，R²代表保护基团，R³代表氢、烷基、芳基、芳基烷基、烷基芳基、杂原子烷基或杂原子芳基基团，在该过程中，使用具有以下结构的两性物质： A-E   IV 其中A代表具有5至20个碳原子的非极性烷基链或甘油二烷基醚基团，E代表极性（亲水）基团，例如-O-SO₃Na、-SO₃Na、-O(CH₂CH₂O)nH或-OP⊖O₂/OCH₂CH₂N⊕(CH₃)₃/，其中n为3到15之间的数字。氢化可以在极性或非极性溶剂中进行。
• Diphosphines and Metal Complexes
  申请人：Kesselgruber Martin

  公开号：US20090270622A1

  公开（公告）日：2009-10-29

  Compounds of the formula I or I′, where the radicals R 1 are each, independently of one another, a hydrogen atom or C 1 -C 4 -alkyl and R′ 1 , is C 1 -C 4 -alkyl; X 1 and X 2 are each, independently of one another, a sec-phosphino group; R 2 is hydrogen, R 01 R 02 R 03 Si— is halogen-, hydroxyl-, C 1 -C 8 -alkoxy- or R 04 R 05 N-substituted C 1 -C 18 -acyl or is R 06 —X 01 —C(O)—; R 01 , R 02 and R 03 are each, independently of one another, C 1 -C 12 -alkyl, unsubstituted or C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted C 6 -C 10 -aryl or C 7 -C 12 -aralkyl; R 04 and R 05 are each, independently of one another, hydrogen, C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 10 -aryl or C 7 -C 12 -aralkyl, or R 04 and R 05 together are trimethylene, tetramethylene, pentamethylene or 3-oxapentylene; R 06 is C 1 -C 18 -alkyl, unsubstituted or C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted C 3 -C 8 -cycloalkyl, C 6 -C 10 -aryl or C 7 -C 12 -aralkyl; X 01 is —O— or —NH—; T is C-bonded C 3 -C 20 -heteroarylene; v is 0 or an integer from 1 to 4; X 1 in the heteroring of the heteroarylene is bound in the ortho position relative to the T—C* bond; and * indicates a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically pure diastereomers. The compounds are excellent chiral ligands for metal complexes as enantioselective catalysts for the hydrogenation of prochiral organic compounds.

  公式I或I'的化合物，其中基团R1分别是氢原子或C1-C4-烷基，R'1是C1-C4-烷基；X1和X2分别是sec-膦基团；R2是氢，R01R02R03Si—是卤素、羟基、C1-C8-烷氧基或R04R05N取代的C1-C18-酰基或是R06—X01—C(O)—；R01、R02和R03分别是C1-C12-烷基、未取代或C1-C4-烷基或C1-C4-烷氧基取代的C6-C10-芳基或C7-C12-芳基烷基；R04和R05分别是氢、C1-C12-烷基、C3-C8-环烷基、C6-C10-芳基或C7-C12-芳基烷基，或者R04和R05一起是三亚甲基、四亚甲基、五亚甲基或3-氧代戊亚甲基；R06是C1-C18-烷基，未取代或C1-C4-烷基或C1-C4-烷氧基取代的C3-C8-环烷基、C6-C10-芳基或C7-C12-芳基烷基；X01是—O—或—NH—；T是C键合的C3-C20-杂芳烃；v是0或1到4之间的整数；杂芳烃的异环中X1与T—C*键的正交位置相结合；*表示混合的外消旋或对映纯二对映异构体或纯外消旋或对映纯二对映异构体。这些化合物是金属配合物的优秀手性配体，用作对手性选择性催化剂，用于对不对称有机化合物的氢化。
• Chiral monophosphites as ligands for assymetrical synthesis
  申请人：——

  公开号：US20030171608A1

  公开（公告）日：2003-09-11

  Certain chiral monophosphites and their monothio derivatives are suitable as ligands in the asymmetrical transition-metal-catalyzed hydrogenation, hydroborination and hydrocyanation of prochiral olefins, ketones and imines.

  某些手性磷酸单酯及其单硫衍生物适用作为配体，在不对称过渡金属催化的氢化、氢硼化和氰化反应中，对非手性烯烃、酮和亚胺进行催化。
• Ferrocenyl diphosphines and their use
  申请人：——

  公开号：US20030212284A1

  公开（公告）日：2003-11-13

  Compounds of the formula (I) and (Ia) in the form of racemates, mixtures of diastereomers or in essentially enantiomerically pure form, (I), (Ia), where R is hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloakyl, phenyl or phenyl substituted by from 1 to 3 C 1 -C 4 alky or C 1 -C 4 alkoxy groups; n is 0 or an integer from 1 to 4 and R 1 are identical or different subtitutuents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl and C 1 -C 4 alkoxy; X 1 and X 2 are each, indenpendently of one another, secondary phosphino; T is C 6 -C 20 arylene or C 3 -C 16 heteroarylene; and X 2 is bound in the ortho position relative to the T-cyclopenitadienyl bond. The compounds are ligands for complexes of metal selected from transition groups (I) and (VIII) of the Periodic Table of the Elements, and these metal complexes are valuable catalysts for the asymmetric addition of hydrogen, boron hydrides or silanes onto carbon-carbon or carbon-heteroatom multiple bonds in prochiral organic compounds or the asymmetric addition of carbon nucleophiles or amines onto allyl compounds. 1

  公式（I）和（Ia）的化合物，以外消旋体、不对映异构体混合物或基本上对映纯形式存在，其中（I），（Ia）中，R是氢，C1-C8烷基，C5-C12环烷基，苯基或由1到3个C1-C4烷基或C1-C4烷氧基取代的苯基；n为0或1到4的整数，R1为选择自C1-C4烷基，C1-C4氟代烷基和C1-C4烷氧基的相同或不同的取代基；X1和X2各自独立于彼此，为次磷酸二烷基；T为C6-C20芳基或C3-C16杂芳基；且X2在相对于T-环戊二烯基键的邻位上结合。这些化合物是从元素周期表的过渡金属（I）和（VIII）组中选择的金属配合物的配体，这些金属配合物是用于对手性有机化合物的碳-碳或碳-杂原子多重键进行氢、硼氢化物或硅烷的不对称加成，或用于对烯丙基化合物进行碳亲核或胺的不对称加成的有价值的催化剂。