CN108727290A - 一种手性噁唑啉钯配合物及用途 - Google Patents

一种手性噁唑啉钯配合物及用途 Download PDF

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CN108727290A
CN108727290A CN201810324053.7A CN201810324053A CN108727290A CN 108727290 A CN108727290 A CN 108727290A CN 201810324053 A CN201810324053 A CN 201810324053A CN 108727290 A CN108727290 A CN 108727290A
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罗梅
彼得·史唐
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Hefei University of Technology
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Abstract

一种手性钯氮配合物，其化学式如下：该配合物的合成方法，由邻二氰基苯50.75mmol和D‑苯甘氨醇21.4037g在无水无氧条件下和无水ZnCl224.7mol％于氯苯溶剂中回流反应60小时，然后纯化，用石油醚及二氯甲烷按体积比4：1淋洗，柱层析分离，自然挥发得噁唑啉；再将噁唑啉与氯化钯按1:1.49摩尔比在氯苯溶剂中回流反应48小时后脱去氯苯，得红褐色固体，加入三氯甲烷及乙醇溶液过滤，自然挥发得配合物单晶；称取该钯配合物0.6774g，加入三氟甲磺酸银2.3297g,二氯甲烷30mL室温反应48h,停止反应,过滤后，再加入三氯甲烷及乙醇溶解，自然挥发，得黑色晶体；该手性钯氮配合物的用途，在苯甲醛的亨利反应、腈硅化反应及Baylis‑Hillman反应中显示一定的催化性能，其转化率分别达58％，89％及62％。

Description

一种手性噁唑啉钯配合物及用途
一、技术领域
本发明涉及一种金属有机配位化合物(配合物)及其用途，特别涉及含氮的手性金属有机配合物及用途，确切地说是一种手性噁唑啉钯金属有机配合物及其用途。
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。近年来手性锌噁唑啉钯金属配合物在不对称催化领域取得了一定的催化效果。
参考文献：
1.Highly enantioselective Pd(II)-catalyzed Wacker-type cyclization of2-allylphenols by use of bisoxazoline ligands with axis-unfixed biphenylbackbone Wang,Feijun et al,Tetrahedron Letters,48(24),4179-4182；2007
2 Incorporation of a Phebox Rhodium Complex into apo-MyoglobinAffords a Stable Organometallic Protein Showing Unprecedented Arrangement ofthe Complex in the Cavity Satake,Yuh；Abe,Satoshi；Okazaki,Seiji；Ban`,Noritaka；Hikage,Tatsuo；Ueno,Takafumi；Nakajima,Hiroshi；Suzuki,Atsuo；Yamane,Takashi；Nishiyama,Hisao；et al,Organometallics(2007),26(20),4904-4908.
3.Novel chiral bisoxazoline ligands with a biphenyl backbone:preparation,complexation,and application in asymmetric catalytic reactions ByImai,Yoshitane；Zhang,Wanbin；Kida,Toshiyuki；Nakatsuji,Yohji；Ikeda,Isao,Journalof Organic Chemistry(2000),65(11),3326-3333.
4.Rhodium(III)and Rhodium(II)Complexes of Novel Bis(oxazoline)PincerLigands Gerisch,Michael；Krumper,Jennifer R.；Bergman,Robert G.；Tilley,T.Don,Organometallics(2003),22(1),47-58.
5.Synthesis of optically active bis(2-oxazolines):crystal structureof a 1,2-bis(2-oxazolinyl)benzene·zinc chloride complex，Bolm,Carsten；Weickhardt,Konrad；Zehnder,Margareta；Ranff,Tobias Chemische Berichte(1991),124(5),1173-80.
6.Reactions of perfluoroalkanesulfonic acids.II.Chemistry ofperfluoroalkanesulfonic acids,Schmeisser,Martin；Sartori,Peter；Lippsmeier,Bernd,Chemische Berichte(1970),103(3),868-79。
三、发明内容
本发明旨在提供一种Pd-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邻遴选相应的原料并建立相应的方法合成手性催化剂。
本发明所称的手性钯氮配合物是由以下化学式(I)所示的配合物：
化学名称：一水合二-三氟甲磺酸酸基双[1,2-(4R)-二苯基－2－噁唑啉基苯]钯配合物，R:Ph,简称配合物(I)。
本手性配合物(I)的合成方法包括反应、分离和纯化，其特征是由邻二氰基苯50.75mmol和D-苯甘氨醇21.4037g在无水无氧条件下和催化剂无水ZnCl2(24.7mol％)于氯苯溶剂中回流反应60小时，然后分离、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；用石油醚及二氯甲烷(4：1)淋洗，柱层析分离，自然挥发得配体噁唑啉；再将手性配体噁唑啉与氯化钯按照1:1.49摩尔比在氯苯溶剂中回流反应48小时，反应结束后脱去氯苯，得红褐色固体，加入三氯甲烷及乙醇溶液过滤后，自然挥发滤液得红褐色噁唑啉钯配合物单晶；称取双[1,2-(4R)-二苯基－2－噁唑啉基苯]氯化钯配合物0.6774g,，加入三氟甲磺酸银2.3297g,二氯甲烷30mL将混合物室温反应48h,停止反应,过滤后，再加入三氯甲烷及乙醇溶解，自然挥发，得黑色配合物晶体。
该配合物在苯甲醛的亨利反应、腈硅化反应及Baylis-Hillman反应中显示一定的的催化性能，其转化率分别达58％，89％及62％。
四、附图说明
图1是一水合二-三氟甲磺酸酸基双[1,2-(4R)-二苯基－2－噁唑啉基苯]钯配合物(I)的单晶衍射图。
五、具体实施方式
(一)手性配合物的制备
1.[1,2-(4R)-二苯基－2－噁唑啉基]苯的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl21.7109g(12.55mmol),40ml氯苯,1,2-二氰基苯6.5031g(50.75mmol),D-苯甘氨醇21.4037g,将混合物在高温下回流24h,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(4:1)柱层析,得浅绿色粘稠状液体[a]5 D＝-64.8°(c＝0.52,CHCl3)；1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝7.86～7.89(m,2H),7.52～7.55(m,2H),7.23～7.36(m,10H),4.49～4.59(m,2H),4.21～4.27(t,J＝0.61Hz,2H),3.99～4.03(t,J＝0.84Hz,2H),3.14～3.20(dd,J＝5.57,5.48Hz,2H),2.73～2.75(dd,J＝4.24,4.27Hz,2H).13CNMR,41.23,67.89,72.03,126.27,128.24,128.32,129.06,129.20,129.61,130.19,137.83,163.92.IR:3061,3029,2956,2924,2897,2854,1651,1601,1494,1470,1454,1356,1313,1303,1236,1090,1054,1032,971,950,901,893,758,700.HRMS(EI):m/z(％):calcd for C24H20N2O2:368.1525；found:368.1479。
2.[1,2-(4R)-二苯基－2－噁唑啉基苯]氯化钯配合物的制备
100mL两口瓶中,无水无氧条件下,加入氯化钯0.8733g(4.92mmol),1,2-(4R)-二苯基－2－噁唑啉基苯1,.2145g(3..30mmol)，氯苯30mL将混合物在高温下回流48h,停止反应,减压以除去溶剂,,将剩余物三氯甲烷及乙醇溶解，自然挥发，得红褐色配合物得晶体，产率56％；m.p.:208-210℃,[a]5 D＝-1263.7°(c＝0.0364,CHCl3)：1HNMR(600MHz,CDCl3,27℃),δ(ppm)＝8.01-8.13(m,5H),7.62-7.69(s，1H),7.10-7.35(m,6H),5.57(t,J＝0.6Hz,1H)，5.22(t,J＝0.6Hz，1H),4.97(t,J＝0.3Hz,1H),3.58-4.76(m,2H),4.34-4.38(m,1H),13CNMR：69.2,71.5,76.4,76.9,125.7,126.4,128.5,129.1,129.3,129.5,129.7,129.9,120.0,130.1,130.3,130.9,131.0,133.9,134.0,136.9,140.0,147.0,164.9,166.7；元素分析C24H20N2Cl2O2Zn C:52.19％,H,3.48％,N,5.31％；计算值：C:52.82％,H,3.69％,N,5.13％；IR:3030,2161,1979,1711，1629,1592，1494，1454，1377，1315，1278，1233，1207，1128，1070，1042，1029,930，917，761，719，699，651，592。
2.二-三氟甲磺酸基-双[1,2-(4R)-二苯基－2－噁唑啉基苯]钯配合物的制备
100mL两口瓶中,无水无氧条件下,加入三氟甲磺酸银2.3297g,双[1,2-(4-苯基)-二苯基－2－噁唑啉基苯]氯化钯配合物0.6774g,，二氯甲烷30mL将混合物室温反应48h,停止反应,过滤后，再加入三氯甲烷及乙醇溶解，自然挥发，得黑色配合物晶体，产率75％；m.p.:>240℃,[a]5 D＝-14.4°(c＝0.0364,CH2Cl2)：1HNMR(300MHz,CDCl3,27℃),δ(ppm)＝7.98～8.28(m,8H),7.14～7.49(m,20H),6.23～6.26(m,4H),5.38～5.46(m,4H),4.63～4.85(m,4H),3.90(s,2H)；13CNMR(75MHz,CDCl3 27℃)167.8(x2),167.6(x2),138.6(x4)，134.6(x4),132.9(x2),132.4(x2),130.2(x4),130.1(x4),130.0(x4),129.9(x4),129.3(x4),128.9(x4)，124.0(x2)，77.3(x2),74.0(x2)，70.1(x2),69.1(x2)；19FNMR(282MHz，CDCl3 27℃)70.8；元素分析C50H42F6N4O11S2Pd，C:51.58％；H:3.53％；N:4.51％；计算值：C:51.80％,H:3.65％,N:4.83％；ESI m+1/e:计算值:1159.4334；测试值：1159.3940；IR:3448,3205,2954,2924，2854,1705,1621,1557,456,1399，1385，1377，1257，1174,1075,1033,764，720，700，640，576,518。
配合物(I)晶体数据如下：
经验式 C50H42F6N4O11S2Pd
分子量 1159.39
温度 133(2)K
波长
晶系，空间群 单斜晶系,P2(1)
晶胞参数 α＝90°.
β＝107.146(2)°
γ＝90°.
体积 2443.2(4)A^3
电荷密度 2,1.576Mg/m^3
吸收校正参数 0.554mm^-1
单胞内的电子数目 1180
晶体大小 0.211x 0.165x 0.121mm
Theta角的范围 1.911to 25.494
HKL的指标收集范围 -13<＝h<＝13,-17<＝k<17,-15<＝l<＝9
收集/独立衍射数据 17264/8896[R(int)＝0.0514]
theta＝30.5的数据完整度 100.0％
吸收校正的方法 多层扫描
最大最小的透过率 0.7461and 0.6748
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 8896/119/664
精修使用的方法 1.028
衍射点的一致性因子 R1＝0.0855，wR2＝0.1859
可观察衍射的吻合因子 R1＝0.1244,wR2＝0.2130
绝对构型参数 0.00(3)
差值傅里叶图上的最大峰顶和峰谷 2.646and-1.818e.A^-3
晶体典型的键长数据：
晶体典型的键角数据：
(二)、亨利反应应用
1.E-β-硝基苯乙烯的制备
取0.15mmol配合物(I)(催化用量为15％)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48小时，用石油醚/二氯甲烷淋洗，进行柱层析,产率58％；
(三)、腈硅化反应应用
2-苯基-2-(三甲硅氧基)乙腈的制备
0.15mmol化合物I,苯甲醛0.1mL,TMSCN 0.3ml(3.3mmol)相继在20～30℃下加入，48h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：89％，1HNMR(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)。
(四)Baylis-Hillman反应应用
取0.20mmol的配合物I(催化用量为20％)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：62％；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)。

Claims (4)

1.一种手性钯氮配合物，其化学式如下：
2.权利要求1所述的手性钯氮配合物(I)，在293(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，其特征在于晶体属单斜晶系,P2(1)晶胞参数： α＝90°；β＝107.146(2)； γ＝90°。
3.权利要求1所述的手性钯氮配合物(I)的合成方法，包括合成和分离，其特征是由邻二氰基苯50.75mmol和D-苯甘氨醇21.4037g在无水无氧条件下和催化剂无水ZnCl2(24.7mol％)于氯苯溶剂中回流反应60小时，然后分离、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；用石油醚及二氯甲烷按体积比4：1淋洗，柱层析分离，自然挥发得配体噁唑啉；再将手性配体噁唑啉与氯化钯按照1:1.49摩尔比在氯苯溶剂中回流反应48小时，反应结束后脱去氯苯，得红褐色固体，加入三氯甲烷及乙醇溶液过滤后，自然挥发滤液得红褐色噁唑啉钯配合物单晶；称取双[1,2-(4R)-二苯基－2－噁唑啉基苯]氯化钯配合物0.6774g,，加入三氟甲磺酸银2.3297g,二氯甲烷30mL将混合物室温反应48h,停止反应,过滤后，再加入三氯甲烷及乙醇溶解，自然挥发，得黑色配合物晶体。
4.权利要求1所述的手性钯氮配合物(I)的用途，该配合物在苯甲醛的亨利反应、腈硅化反应及Baylis-Hillman反应中显示一定的的催化性能，其转化率分别达58％，89％及62％。
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Cited By (2)

* Cited by examiner, † Cited by third party
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CN108658802A (zh) * 2018-04-23 2018-10-16 苏州大学 一种手性双[n,o]环钯配合物及其合成方法
CN110669023A (zh) * 2019-10-17 2020-01-10 合肥工业大学 一种手性噁唑啉铜配合物的用途

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CN104628788A (zh) * 2015-02-11 2015-05-20 罗梅 一种手性噁唑啉钯配合物及用途
CN105198935A (zh) * 2015-10-02 2015-12-30 合肥祥晨化工有限公司 一种手性噁唑啉钯配合物

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CN104628788A (zh) * 2015-02-11 2015-05-20 罗梅 一种手性噁唑啉钯配合物及用途
CN105198935A (zh) * 2015-10-02 2015-12-30 合肥祥晨化工有限公司 一种手性噁唑啉钯配合物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108658802A (zh) * 2018-04-23 2018-10-16 苏州大学 一种手性双[n,o]环钯配合物及其合成方法
CN108658802B (zh) * 2018-04-23 2020-10-09 苏州大学 一种手性双[n,o]环钯配合物及其合成方法
CN110669023A (zh) * 2019-10-17 2020-01-10 合肥工业大学 一种手性噁唑啉铜配合物的用途
CN110669023B (zh) * 2019-10-17 2022-11-29 合肥工业大学 一种手性噁唑啉铜配合物的用途

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Application publication date: 20181102