CN105218473B - 一种含甲醇结晶的手性锌配合物 - Google Patents

一种含甲醇结晶的手性锌配合物 Download PDF

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CN105218473B
CN105218473B CN201510669341.2A CN201510669341A CN105218473B CN 105218473 B CN105218473 B CN 105218473B CN 201510669341 A CN201510669341 A CN 201510669341A CN 105218473 B CN105218473 B CN 105218473B
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罗梅
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Abstract

一种含甲醇结晶的手性锌配合物,其化学式如下:（I）。该配合物晶体的合成方法，是由四氰乙烯和D‑苯丙氨醇在无水无氧条件下和催化剂无水ZnCl2 (65%)时于氯苯溶剂中回流反应60小时离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；配合物（I）用石油醚及二氯甲烷淋洗，柱层析分离，自然挥发得配合物单晶。

Description

一种含甲醇结晶的手性锌配合物
一、技术领域
本发明涉及一种金属有机配位化合物(配合物)及其制备方法，特别涉及含氮的手性金属有机配合物及其制备方法，确切地说是一种手性D-型锌氮配合物及其合成方法。
二、背景技术
随着有机化学的发展,金属有机化合物在有机合成中的应用愈来愈广,是现在有机化学中极为活跃的领域之一,已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性配体及含金属催化剂的设计,从而使反应具有高效和高对映选择性。通常不对称催化剂所用的配体是噁唑啉，近年来噁唑啉锌配合物被广泛合成并取得较好的催化效果，见参考文献【1-4】：
参考文献：
1.Ir(I)complexes with oxazoline-thioether ligands:nucleophilic attackof pyridine on coordinated 1,5-cyclooctadiene and application as catalysts inimine hydrogenation,Guiu,Ester；Claver,Carmen；Castillon,Sergio,Journal ofOrganometallic Chemistry,689(11),1911-1918。
Jiang,M.；Dalgarno,S.；Kilner,C.A.；Halcrow,M.A.；Kee,T.P.Polyhedron,20(17),2151-2162。
Ito,Jun-ichi；Ujiie,Satoshi；Nishiyama,Hisao,Organometallics,28(2),630-638.
4.Lewis Acid-Catalyzed Enantioselective Hydroxylation Reactions ofOxindoles andβ-Keto Esters
Using DBFOX Ligand，Ishimaru,Takehisa；Shibata,Norio；Nagai,Jun；Nakamura,Shuichi；Toru,Takeshi；
Kanemasa,Shuji,Journal of the American Chemical Society，128(51),6488-16489。
三、发明内容
本发明旨在提供一种Zn-N金属有机配合物以应用于催化领域，所要解决的技术问题遴选噁唑啉作为配体并合成手性锌氮配合物。
本发明所称的手性锌配合物是双-(4-苄基-4,5-二氢化-2-噁唑啉基)-乙腈锌配合物由四氰乙烯制备的由以下化学式所示的配合物：
化学名称：双-(4-苄基-4,5-二氢化-2-噁唑啉基)-乙腈锌配合物，简称配合物(I)。
本配合物(I)的合成方法包括反应、分离和纯化，其特征是由四氰乙烯和D-苯丙氨醇在无水无氧条件下和催化剂无水ZnCl2(65％)时于氯苯溶剂中回流反应60小时离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；
本配合物(I)的合成方法是四氰乙烯与D-苯丙氨醇在氯苯溶剂中回流反应60小时；
配合物(I)用石油醚及二氯甲烷淋洗，柱层析分离，自然挥发得配合物单晶。
该配合物的反应机理可推测为四氰乙烯在空气中及氯化锌作用下，不稳定，分解成三腈基甲烷，与2分子的D-苯丙氨醇作用形成双噁唑啉再与氯化锌按照2:1配位，并脱去两分子盐酸。
四、附图说明
图1是配合物(I)的单晶衍射图。
五、具体实施方式
(一)手性配合物的制备
双-(4-苄基-4,5-二氢化-2-噁唑啉基)-乙腈锌配合物的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl2 0.7533g(5.89mmol),40mL氯苯,四氰乙烯1.0890g(8.51mmol),D-苯丙氨醇11.0398g,将混合物在高温下回流60h,停止反应,减压以除去溶剂,,将剩余物用水溶解,并用CHCl3(20mLx2)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂,将粗产品用石油醚/二氯甲烷(1:4)柱层析,得白色固体，并用甲醇/正己烷重结晶，得白色晶体，产率75％；m.p.：146-148℃,[a]5 D＝-60.8°(c＝0.39,CH3OH)：IR:3448,3027,2921,2201,1611,1529,1453,1432,1368,1343,1260,1223,1087,966,744,702,524,503；元素分析C88H84N12O9Zn测试值C:66.55％,H,5.26％,N,10.18％；计算值：C:66.96％,H,5.30％,N,10.53％；晶体结构数据如下：
晶体典型的键长数据：
晶体典型的键角数据：
(二)、腈硅化反应应用
2-苯基-2-(三甲硅氧基)丙腈
0.1mmol配合物I,苯甲醛0.1mL,TMSCN 0.3ml(3.3mmol),2mL二氯甲烷相继在20～30℃下加入，30小时后，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,产率分别为：68％；1H NMR(300MHz,CDCl3)7.56–7.59(m,0.9Hz,2H),7.31–7.34(m,3H),5.43(s,1H),0.16(s,9H).13C NMR(75MHz,CDCl3)136.1,128.8(x2),126.2(x2),119.1,63.5,-0.39(x3)。
(三)烯丙基烷基化反应应用
取0.10mmol的配合物I(催化用量为10％)于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.3mL的烯丙基三甲基硅烷，常温搅拌，反应48小时后，进行核磁分析，转化率：62％；1H NMR(300MHz,CDCl3)7.27～7.33(m,5H,Ar-H),5.79～5.80(m,1H),5.12～5.17(m,2H,-CH2),4.71(d，J＝5Hz，1H),2.49～2.50(m,2H)，2.28(s,1H)。
(四)Baylis-Hillman反应应用
取0.10mmol的配合物I(催化用量为10％)于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL丙烯酸甲酯，常温搅拌，反应小48小时后，进行核磁分析，转化率：58％；1HNMR(300MHz,CDCl3)7.20～7.41(m,5H,Ar-H),6.30(s,1H),5.45(s,1H),3.70(s,3H),3.15(s,1H)。
(五)亨利反应应用
2-硝基-1苯基乙醇的制备
取0.10mmol的配合物I(催化用量为10％)于25mL的小烧瓶中，加入2毫升的无水甲醇溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL的硝基甲烷，常温搅拌，反应小48小时后，进行核磁分析，转化率：75％；1H NMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH)。
申请人平行条件下，做了类似配合物的腈硅化反应，亨利反应，烯丙基烷基化反应及baylis-Hillman反应，其结果见以下表格，类似配合物的结构式如下：
平行条件下，催化反应结果如下：

Claims (2)

1.一种如化学式(I)所示的含甲醇结晶的手性锌配合物,其晶胞参数如下，在296(2)K温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线，以ω-θ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)，晶胞参数 α＝90°；β＝90.917(6)°；γ＝90°；
2.权利要求1所述的含甲醇结晶的手性锌配合物晶体的合成方法，包括合成和分离，由四氰乙烯和D-苯丙氨醇在无水无氧条件下和65％催化剂无水ZnCl2于氯苯溶剂中回流反应60小时分离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；配合物(I)用石油醚及二氯甲烷淋洗，柱层析分离，自然挥发得配合物单晶。
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