CN102659706B - 一种手性噁唑啉的制备及合成方法 - Google Patents

一种手性噁唑啉的制备及合成方法 Download PDF

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CN102659706B
CN102659706B CN201210116668.3A CN201210116668A CN102659706B CN 102659706 B CN102659706 B CN 102659706B CN 201210116668 A CN201210116668 A CN 201210116668A CN 102659706 B CN102659706 B CN 102659706B
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CN102659706A (zh
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罗梅
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Abstract

一种手性噁唑啉的制备，其化学式如下：

Description

一种手性噁唑啉的制备及合成方法
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种手性化合物及其制备方法，确切地说是一种手性噁唑啉的制备及合成方法。
二、背景技术
手性噁唑啉是重要的医药化工产品及催化剂，近年来，国内外最新报道了种类繁多的双齿，三齿及四齿噁唑啉对氢化反应、Heck反应、烯丙基烷基化反应、Diels-Alder反应，二乙基锌对醛的加成反应等具有非常好的催化活性。【1-13】
参考文献：
1.Cozzi,P.G.；Menges,F.；Kaiser,S.Iridium-HetPHOX complexes for the catalytic asymmetrichydrogenation of olefins and imines,Synlett,2003,833-836.
2.Tang,W.J.；Wang,W.M；Zhang,X.M..Phospholane–Oxazoline Ligands for Ir-CatalyzedAsymmetric Hydrogenation,Angew.Chem.,Int.Ed.Engl.2003,42,943.
3.Hilgraf,R.；Pfaltz,A.Chiral bis(N-tosylamino)phosphine-and TADDOL-phosphite-oxazolines as ligands in asymmetric catalysisSynlett.1999,1814-1816.
4.(a)Powell,M.T.；Hou,D.-R.；Perry,M.C.；Cui,X.；Burgess,K.Chiral ImidazolylidineLigands for Asymmetric Hydrogenation of Aryl Alkenes,J.Am.Chem.Soc.2001,123,8878-8879.(b)Perry,M.C.；Cui,X.；Powell,M.T.；Hou,D.-R.；Reibenspies,J.H.；Burgess,K.Optically
Active Iridium Imidazol-2-ylidene-oxazoline Complexes:Preparation and Use inAsymmetric
Hydrogenation of Arylalkenes,J.Am.Chem.Soc.2003,125,113-123.
5.Gilbertson,Scott.R.；Xie,D.J.；Fu,Z.,Proline derived phosphine–oxazoline ligands in theasymmetric Heck reaction,Tetrahedron Lett.2001,42,365-368.
6.Hashimoto,Y.；Horie,Y.；Hayashi,M.；Saigo,K.An efficient phosphorus-containingoxazoline ligand derived from cis-2-amino-3,3-dimethyl-1-indanol:application to thepalladium-catalyzed asymmetric Heck reaction Tetrahedron:Asymmetry 2000,11,2205-2210.
7.Tu,T.；Deng,W.-P.；Hou,X.-L.；Dai,L.-X.；Dong,X.-C.The regioselectivity of theasymmetric intermolecular Heck reaction with planar chiral diphosphine-oxazolineferrocenyl ligandsChem.Eur.J.2003,9,3073-3081.
8.Gilbertson,S.R.；Xie,D.Proline-Based P,N Ligands in Palladium-Catalyzed Asymmetricπ-Allyl Addition,Angew.Chem.,Int.Ed.Engl.1999,38,2750-2752.
9.Burgess,K.；Porte,A.M.Application of novel phosphine oxazoline ligands in asymmetricallylations of 4-acyloxy-2-pentene derivatives,Tetrahedron:Asymmetry,1998,9,2465-2469.
10.Bolm,C.；Xiao,L.；Kesselgruber,M.Synthesis of novel chiral phosphinoCyrhetrenyl-oxazoline ligands and their application in asymmetric catalysis,Org.Biomol.Chem.2003,1,145-152.
11.Watanabe,K.；Hirasawa,T.；Hiroi,K.Lewis acid-catalyzed asymmetric diels-alder reactionsusing chiral sulfoxide ligands:Chiral 2-(Arylsulfinylmethyl)-1,3-oxazoline derivatives,Chem.Pharm.Bull.2002,50,372-379.
12.Wipf,P.；Wang,X.D.A new ligand scaffold for catalytic asymmetric alkylzinc additions toaldehydes,Org.Lett.2002,4,1197-1200.
13.Schinnerl,M.；Seitz,M.；Kaiser,A.；Reiser,O.,New applications of bis(oxazoline)ligandsin
catalysis:Asymmetric 1,2-and 1,4-addition of ZnR2 to carbonyl compounds,Org.Lett.2001,3,4259-4262.
申请人以7,7,8,8-四氰基奎二甲烷与L-苯甘氨醇在105mol％氯化锌作催化剂下，得到了一种手性化合物4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈。
一、发明内容
本发明旨在提供手性化合物4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈,所要解决的技术问题是一步合成得到目标产物。
本发明所称的一种手性化合物是由7,7,8,8-四氰基奎二甲烷与L-苯甘氨醇制备的由以下化学式所示的化合物：
化学名称：4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈,简称化合物(I)。
本合成方法包括合成和分离，所述的合成用105mol％氯化锌做催化剂，7,7,8,8-四氰基奎二甲烷4.90mmol，L-苯甘氨醇90mmol，用50mL氯苯做溶剂，回流反应3天后，柱层析分离，用石油醚/二氯甲烷(3/7)洗脱，将收集的最后组分点自然挥发，得单晶4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。该化合物在苯甲醛的腈硅化反应中显示了一定的催化效果，其转化率达48.8％。
其反应机理可推测如下：
7,7,8,8-四氰基奎二甲烷由于在空气及大量路易斯酸催化剂，大大过量的L-苯甘氨醇作用下不稳定，首先经过还原、分解生成了4-氰甲基苯腈，然后与大大过量的L-苯甘氨醇在氯化锌作用下得手性化合物4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈，其反应过程如下:
四、附图说明
图1是4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈的X-衍射分析图。
二、具体实施方式
1.4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈的制备
在100mL两口瓶中,加入无水ZnCl270mg(0.74mmol),50mL氯苯,7,7,8,8-四氰基奎二甲烷1.0g(4.90mmol),L-苯甘氨醇9.3g,将混合物在高温下回流72h,停止反应,减压以除去溶剂,,将剩余物用水溶解,并用CH2Cl2(20mLx3)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(3:7)柱层析,得无色油状液体,产率42％；[a]5 D＝-18.12°(c＝0.0552,CH2Cl2)：1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝8.07(d,J＝10Hz，1H),7.26～7.42(m，7H),5.37～5.42(m,1H),4.79～4.83(m,1H),4.29(t,J＝Hz,1H),3.81(s,2H)；13CNMR(125MHz,CDCl3,27℃)164.1,142.1,133.4,129.3,128.8,127.8,127.6,126.8,117.3,75.0,70.1,23.7；IR(KBr):3061,3030,2947,2854,2249,1723,1648,1614,1579,1514,1494,1475,1455,1416,1356,1334,1318,1302,1277,1252,1179,1181,1113,1073,1021,976,950,936,923,899,824,764,752,721,699,533,483；HRMS:m/z(％):C17H14N2O,calcd for C17H14N2O262.1106；found:262.1105。
(三)、腈硅化反应应用
2-苯基-2-(三甲硅氧基)乙腈
0.1mmol化合物I,苯甲醛0.1mL,TMSCN0.3ml(3.3mmol),2mL二氯甲烷相继在20～30℃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,转化率率:48.8％；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).

Claims (1)

1.一种由以下化学式所示的手性噁唑啉化合物(I)的合成方法，包括合成和分离，其特征在于：所述的合成用105mol％氯化锌做催化剂，7,7,8,8-四氰基奎二甲烷4.90mmol，L-苯甘氨醇66mmol，用50mL氯苯做溶剂，回流反应3天后，柱层析分离，用石油醚/二氯甲烷按体积比为3/7洗脱，将收集的最后组分点自然挥发，得单晶4-[4'(S)-苯基-4,5-二氢化-2-噁唑啉基]-苯乙腈，
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