CN103304586A - 一种手性铜配合物 - Google Patents

一种手性铜配合物 Download PDF

Info

Publication number
CN103304586A
CN103304586A CN2013102821785A CN201310282178A CN103304586A CN 103304586 A CN103304586 A CN 103304586A CN 2013102821785 A CN2013102821785 A CN 2013102821785A CN 201310282178 A CN201310282178 A CN 201310282178A CN 103304586 A CN103304586 A CN 103304586A
Authority
CN
China
Prior art keywords
copper compound
chiral copper
crystal
phenylalaninol
acetate dihydrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013102821785A
Other languages
English (en)
Other versions
CN103304586B (zh
Inventor
罗梅
邹雄斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201310282178.5A priority Critical patent/CN103304586B/zh
Publication of CN103304586A publication Critical patent/CN103304586A/zh
Application granted granted Critical
Publication of CN103304586B publication Critical patent/CN103304586B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种手性铜化合物的制备,其化学式如下：

Description

一种手性铜配合物
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种铜性化合物及其制备方法，确切地说是一种手性L-苯甘氨醇氯化铜配合物的制备及合成方法。
二、背景技术
手性氨基醇铜配合物是重要的催化剂和医药化工产品，其作为催化剂在不对称Henry反应，二乙基锌与苯甲醛对映选择性加成反应等反应中有较好的催化效果。【1-3】
参考文献：
1. Zheng, Bing; Wang, Min; Li, Zhiyuan; Bian, Qinghua; Mao, Jianyou; Li, Shuoning; Liu, Shangzhong; Wang, Mingan; Zhong, Jiangchun; Guo, Hongchao，Asymmetric Henry reaction catalyzed by a Zn-amino alcohol system ，Tetrahedron: Asymmetry， 2011,22（11），1156-1160.
2. Li, Zhi-Yuan; Wang, Min; Bian, Qing-Hua; Zheng, Bing; Mao, Jian-You; Li, Shuo-Ning; Liu, Shang-Zhong; Wang, Ming-An; Zhong, Jiang-Chun; Guo, Hong-Chao, Highly Enantioselective Addition of Trimethylsilylacetylene to Aldehydes Catalyzed by a Zinc-Amino-Alcohol Complex, Chemistry--A European Journal, 2011, 17(21),5782-5786, S5782/1-S5782/85.
3. Kim, Hun-Young; Oh, Kyung-Soo, Brucine-Derived Amino Alcohol Catalyzed Asymmetric Henry Reaction: An Orthogonal Enantioselectivity Approach, Organic Letters, 2009,11(24),5682-5685。
三、发明内容
本发明旨在提供手性四[（S）-苯丙氨醇]氯化铜配合物。所要解决的技术问题是一步合成得到目标产物。
本发明所称的手性铜配合物是由二水合氯化铜与(S)-苯丙氨醇制备的由以下化学式所示的化合物：
Figure 802807DEST_PATH_IMAGE001
（I）。
化学名称：四[（S）-苯丙氨醇]氯化铜配合物,简称配合物(I)。该化合物在苯甲醛的腈硅化反应中显示了一定的催化性能，其转化率达26.1%。
本合成方法包括合成和分离，所述的合成（S）-苯丙氨醇与二水合氯化铜以摩尔比3：1的比例进行反应，用电子天平称取(S)-苯丙氨醇2.265g(0.015mol)和二水合氯化铜0.8524g(0.005mol)，加入到100ml的圆底烧瓶中，再加约35ml的无水乙醇作溶剂，加热、搅拌回流48h，趁热过滤，将滤液旋干，換溶剂配成饱和溶液，静置、自行挥发，滤渣同上处理。一段时间后，析出适合用于X-单晶衍射测试的淡蓝色晶体。
用石油醚充分冲洗3-4次，真空干燥30min，得到较纯的目标产物。
合成反应如下：
Figure 657631DEST_PATH_IMAGE002
本合成方法一步得到目标产物，工艺简单，操作方便。
四、附图说明
图1是手性L-苯丙氨醇铜配合物的X-衍射分析图。
五、具体实施方式
手性L-苯丙氨醇氯化铜配合物的制备：
（S）-苯丙氨醇与二水合氯化铜以摩尔比3：1的比例进行反应，用电子天平称取（S）-苯丙氨醇2.265g(0.015mol)和二水合氯化铜0.8524g(0.005mol)，加入到100ml的圆底烧瓶中，再加约35ml的无水乙醇作溶剂，加热、搅拌回流48h，趁热过滤，将滤液旋干，換溶剂配成饱和溶液，静置、自行挥发，滤渣同上处理。一段时间后，析出适合用于X-单晶衍射测试的淡蓝色晶体;用石油醚充分冲洗3-4次，真空干燥30min，得到较纯的目标产物，熔点为132-134℃。α=-110.76°(c 0.0632, CH3OH), 元素分析（C36H50Cl2Cu2N4O4）理论值：C：53.994%；N：6.996%；H：6.293% ;实测值：C：53.83%；N：7.04%；H：6.37%；IR(cm-1), 3340, 3123, 2923，1571, 1488，1446, 1054, 745，513。
化合物的晶体数据：
经验式 C36H50N4 O4Cl2 Cu2
分子量 800.78
温度 140(2) K
波长 1.54178 A
晶系， 空间群 三斜晶系, P2(1) 2(1)2(1)
晶胞参数 a = 9.5750(2) A alpha = 90deg.
b = 10.6789(2) A beta = 90deg.
c = 35.7441(7) A gamma = 90deg.
体积 3654.85（4）A^3
电荷密度 4, 1.455Mg/m^3
吸收 校正参数 3.130 mm^-1
单胞内的电子数目 1672
晶体大小 0.12x 0.02x 0.01 mm
Theta 角的范围 4.32 to 69.43
HKL的指标收集范围 -11<=h<=9, -12<=k<12, -43<=l<=40
收集/独立衍射数据 19922/ 6521 [R(int) = 0.0738]
theta = 30.5的数据完整度 96.2 %
吸收校正的方法 多层扫描
最大最小的透过率 0.8869 and 0.7486
精修使用的方法 F^2 的矩阵最小二乘法
数据数目/使用限制的数目/参数数目 6521/0/434
精修使用的方法 1.046
衍射点的一致性因子 R1 = 0.0521，wR2= 0.1523
可观察衍射的吻合因子 R1 = 0.0594, wR2 = 0.1588
绝对构型参数 0.03（3）
差值傅里叶图上的最大峰顶和峰谷 0.847 and -0.705 e.A^-3
晶体典型的键长数据：
Cu(1)-O(3) 1.954(3)
Cu(1)-O(2) 1.973(3)
Cu(1)-N(2) 2.006(4)
Cu(1)-N(1) 2.035(4)
Cu(1)-O(1) 2.392(4)
Cu(1)-Cu(2) 2.8628(10)
Cu(2)-O(3) 1.978(3)
Cu(2)-O(2) 1.990(3)
Cu(2)-N(3) 2.010(4)
Cu(2)-N(4) 2.030(4)
Cu(2)-Cl(2) 2.5800(13)
晶体典型的键角数据
O(3)-Cu(1)-O(2) 80.44(14)
O(3)-Cu(1)-N(2) 165.55(16)
O(2)-Cu(1)-N(2) 85.13(16)
O(3)-Cu(1)-N(1) 98.89(16)
O(2)-Cu(1)-N(1) 174.46(17)
N(2)-Cu(1)-N(1) 95.39(17)
O(3)-Cu(1)-O(1) 87.47(14)
O(2)-Cu(1)-O(1) 109.02(14)
N(2)-Cu(1)-O(1) 98.08(16)
N(1)-Cu(1)-O(1) 76.39(16)
O(3)-Cu(1)-Cu(2) 43.59(10)
O(2)-Cu(1)-Cu(2) 43.97(10)
N(2)-Cu(1)-Cu(2) 123.04(13)
N(1)-Cu(1)-Cu(2) 132.72(13)
O(1)-Cu(1)-Cu(2) 118.66(9)
O(3)-Cu(2)-O(2) 79.48(14)
O(3)-Cu(2)-N(3) 85.43(15)
O(2)-Cu(2)-N(3) 164.54(15)
O(3)-Cu(2)-N(4) 154.31(16)
O(2)-Cu(2)-N(4) 96.21(17)
N(3)-Cu(2)-N(4) 95.95(18)
O(3)-Cu(2)-Cl(2) 102.93(11)
O(2)-Cu(2)-Cl(2) 98.09(10)
N(3)-Cu(2)-Cl(2) 88.48(13)
N(4)-Cu(2)-Cl(2) 102.75(14)
O(3)-Cu(2)-Cu(1) 42.96(10)
O(2)-Cu(2)-Cu(1) 43.52(9)
N(3)-Cu(2)-Cu(1) 121.43(12)
N(4)-Cu(2)-Cu(1) 119.18(14)
Cl(2)-Cu(2)-Cu(1) 122.36(4)
（三）、腈硅化反应应用
2- 苯基 -2- （三甲硅氧基）丙腈
Figure 437368DEST_PATH_IMAGE003
0.15mmol 化合物I, 苯甲醛0.1mL, TMSCN 0.3 mL (3.3mmol), 2mL THF, 相继在20~30˚C下加入，5天后， 加入水淬灭经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体, 转化率：26.1 %；1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。

Claims (3)

1.一种手性铜配合物的制备是由一水合乙酸铜与L-苯丙氨醇反应，由以下化学式所示的化合物：
（I）。
2.由权利要求1所述的配合物(I)，在140（2）k温度下，在Oxford X-射线单晶衍射仪上，用经石墨单色器单色化的MoKa射线（λ=0.71073 A）以w-Theta 扫描方式收集衍射数据，其特征在于晶体属斜方晶系,空间群 P2(1)2(1)2(1), a = 9.5750(2) A alpha = 90 deg; b = 10.6789(2) A beta = 90 deg;c = 35.7441(7) A gamma = 90 deg。
3.
由权利要求1所述的配合物(I)的合成方法，包括合成和分离，其特征在于所述的合成用S-缬氨醇与一水合乙酸铜以摩尔比3:1进行反应，称取S-缬氨醇2.4756g(0.024mol)、一水合乙酸铜1.5972g（0.08mol），甲苯40ml于100mL圆底烧瓶中，加热搅拌回流48h，热过滤，滤液静置，将油状滤渣溶于无水甲醇中，静置挥发，几天后析出适合与X-单晶衍射的浅绿色晶体。
CN201310282178.5A 2013-07-07 2013-07-07 一种手性铜配合物 Expired - Fee Related CN103304586B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310282178.5A CN103304586B (zh) 2013-07-07 2013-07-07 一种手性铜配合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310282178.5A CN103304586B (zh) 2013-07-07 2013-07-07 一种手性铜配合物

Publications (2)

Publication Number Publication Date
CN103304586A true CN103304586A (zh) 2013-09-18
CN103304586B CN103304586B (zh) 2015-07-22

Family

ID=49130342

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310282178.5A Expired - Fee Related CN103304586B (zh) 2013-07-07 2013-07-07 一种手性铜配合物

Country Status (1)

Country Link
CN (1) CN103304586B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432359A (zh) * 2016-09-12 2017-02-22 合肥祥晨化工有限公司 一种手性镍配合物
CN107383111A (zh) * 2017-07-20 2017-11-24 合肥祥晨化工有限公司 一种手性镍配合物晶体及用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731539A (zh) * 2012-07-12 2012-10-17 罗梅 一种手性化合物的制备及合成方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731539A (zh) * 2012-07-12 2012-10-17 罗梅 一种手性化合物的制备及合成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432359A (zh) * 2016-09-12 2017-02-22 合肥祥晨化工有限公司 一种手性镍配合物
CN107383111A (zh) * 2017-07-20 2017-11-24 合肥祥晨化工有限公司 一种手性镍配合物晶体及用途

Also Published As

Publication number Publication date
CN103304586B (zh) 2015-07-22

Similar Documents

Publication Publication Date Title
Xu et al. Cyclometalated Pd (II) and Ir (III) 2-(4-bromophenyl) pyridine complexes with N-heterocyclic carbenes (NHCs) and acetylacetonate (acac): synthesis, structures, luminescent properties and application in one-pot oxidation/Suzuki coupling of aryl chlorides containing hydroxymethyl
CN103342710A (zh) 一种手性锌配合物
Sanford et al. Synthesis, characterization and application of pincer-type nickel iminophosphinite complexes
CN103275108A (zh) 一种手性铜配合物制备及合成方法
Jia et al. Two cadmium (II) complexes with oxazoline-based ligands as effective catalysts for C–N cross-coupling reactions
CN102936204B (zh) 一种手性化合物
CN103304586A (zh) 一种手性铜配合物
CN103450034B (zh) 一种手性镍配合物
CN103193808A (zh) 一种手性锌配合物
Gao et al. Enantioselective synthesis of monofluorinated allylic compounds: Pd-catalyzed asymmetric allylations of dimethyl 2-fluoromalonate using new N-sulfinyl-based ligands
CN110922420A (zh) 5-异烟酰胺吡啶基异钛酸镉配合物及其制备方法和应用
Yang et al. Transition-metal-based (Co2+, Ni2+ and Cd2+) coordination polymers constructed by a polytopic ligand integrating both flexible aliphatic and rigid aromatic carboxylate groups: Aqueous detection of nitroaromatics
CN102863343B (zh) 一种手性（r）-苯甘氨醇盐酸盐的制备及合成方法
CN105566357A (zh) 一种手性l-缬氨酸铜配合物的制备及合成方法
Tang et al. N-Hetercocyclic carbene metallacrown ethers based on 1, 8-dihydroxy-9, 10-anthraquinone: Synthesis, structures and application in situ palladium-catalyzed Suzuki–Miyaura reaction
CN108689892A (zh) 3-磺酰化-二氢茚酮类化合物及其制备方法
CN103145742B (zh) 一种手性噁唑啉锌配合物
CN103570751A (zh) 一种手性亮氨醇铜配合物
CN102977127A (zh) 一种手性化合物
Sun et al. Synthesis of new Schiff base-camphorsulfonyl amide ligands and in situ screening in the asymmetric additions of organozinc reagents to aldehydes
Pou et al. Schiff bases containing ferrocenyl and thienyl units and their utility in the palladium catalyzed allylic alkylation of cinnamyl acetate
CN103539823B (zh) 一种手性镍配合物晶体的制备及合成方法
CN102875416A (zh) 一种手性化合物
CN104892644A (zh) 一种手性d-苯甘氨醇氯化铜配合物的合成方法
Liu et al. Preparation and Intramolecular C C Coupling Reaction for Bis‐benzimidazolium Salt

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150722

Termination date: 20170707

CF01 Termination of patent right due to non-payment of annual fee