CN104876970A - 一种手性双噁唑啉钯配合物晶体及合成方法 - Google Patents

一种手性双噁唑啉钯配合物晶体及合成方法 Download PDF

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CN104876970A
CN104876970A CN201510258705.8A CN201510258705A CN104876970A CN 104876970 A CN104876970 A CN 104876970A CN 201510258705 A CN201510258705 A CN 201510258705A CN 104876970 A CN104876970 A CN 104876970A
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Abstract

一种手性双噁唑啉钯配合物，其化学式如下： （Ⅰ）。该手性配合物(I)的合成方法是由1，4-二氰基苯39.2mmol和L-缬氨醇16.2075g在无水无氧条件下和催化剂无水ZnCl2（26.4mol%）于氯苯溶剂中回流反应60小时，然后分离、纯化，反应结束后脱去氯苯，将粗产品用石油醚/二氯甲烷(4:1)柱层析,得白色噁唑啉晶体,再按照双噁唑啉与氯化钯摩尔比0.7:1，以氯苯为溶剂进行反应，用三氯甲烷、乙醇及正己烷进行重结晶，得红褐色双噁唑啉氯化钯配合物单晶。该手性配合物在苯甲醛的亨利反应、腈硅化反应及Baylis-Hillman反应中显示一定的催化性能，其转化率分别达67.1%，80.1%,36.2%。

Description

一种手性双噁唑啉钯配合物晶体及合成方法
一、技术领域
本发明涉及一种金属有机配位化合物（配合物）及其合成方法，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双噁唑啉钯金属有机配合物晶体及其合成方法。
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。近年来手性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 of 2-allylphenols by use of bisoxazoline ligands with axis-unfixed biphenyl backbone Wang, Feijun et al, Tetrahedron Letters, 48(24), 4179-4182; 2007
2 Incorporation of a Phebox Rhodium Complex into apo-​Myoglobin Affords a Stable Organometallic Protein Showing Unprecedented Arrangement of the 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 By Imai, Yoshitane; Zhang, Wanbin; Kida, Toshiyuki; Nakatsuji, Yohji; Ikeda, Isao ,Journal of Organic Chemistry (2000), 65(11), 3326-3333.
4. Rhodium(III) and Rhodium(II) Complexes of Novel Bis(oxazoline) Pincer Ligands Gerisch, Michael; Krumper, Jennifer R.; Bergman, Robert G.; Tilley, T. Don,Organometallics (2003), 22(1), 47-58。
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：双{[1,4-(4S)-二异丙基－2－噁唑啉基苯]氯化钯}配合物，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1，4-
二氰基苯39.2mmol和L-缬氨醇16.2075g在无水无氧条件下和催化剂无水ZnCl2（26.4 mol%）于氯苯溶剂中回流反应60小时，然后分离、纯化，反应结束后脱去氯苯，将粗产品用石油醚/ 二氯甲烷(4:1)柱层析,得白色噁唑啉晶体,再按照噁唑啉与氯化钯摩尔比0.7:1，以氯苯为溶剂反应，用三氯甲烷、乙醇及正己烷进行重结晶，得红褐色双噁唑啉氯化钯配合物单晶。
该手性配合物在苯甲醛的亨利反应、腈硅化反应及Baylis-Hillman反应中显示一定的催化性能，其转化率分别达67.1%，80.1%, 36%。
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
1.[1,4-(4R)- 二异丙基－ 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ZnCl21.4054g(mmol),40ml氯苯, 1,4-二氰基苯5.0236g(50.75mmol), L-缬氨醇 16.2075g,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(4:1)柱层析,得浅绿色粘稠状液体, 产率52%;白色晶体, 熔:48-50ºC,[a]5 D=+111.9º (c=0.429,CHCl3); 1HNMR (500MHz,CDCl3, 27℃), δ(ppm)=7.97(s,4H), 4.39～4.43(t, 3.18Hz, 1H), 4.09～ 4.15(m, 2H),1.85～1.86(m, 1H), (d, J= 6.24Hz, 6H), 0.86～0.96(d, J=6.24Hz, 6H).13CNMR 18.13, 19.03, 32.85, 70.26, 72.76, 128.10, 128.16, 130.32, 162.82. IR:3273, 2976, 2960, 2932, 2889, 2869, 1643, 1512, 1469, 1408, 1382, 1366, 1350, 1320, 1296, 1276, 1214,1180, 1108, 1077, 1047,1014, 971, 955, 900, 891, 838, 726, 698, 675, 659, 540.HRMS(EI): m/z (%): calcd for C18H24N2O2: 300.1838; found: 300.1833。
双 {[1,4-(4S)- 二异丙基－ 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1.5603g (4.92mmol), 1,4-(4R)-二异丙基－2－噁唑啉基苯 1,.0435g (3..48mmol)，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：82%；m.p.: >200°C, [a]5 D=+514.2º (c=0.0564, CH3OH)：1HNMR (600MHz,CDCl3, 27℃), δ(ppm)=8.86(s, 4H), 4.56-4.64(m， 4H), 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), 4.46-4.48(m, 2H), 2.96-2.98(m, 2H), 1.06-1.12(dd,J=6.6, 7.2Hz, 12H); 13CNMR：168.7, 132.8, 75.2, 72.5, 33.5, 21.5, 18.7; 元素分析C36H50N4Cl4O5Pd2 实测值：C: 44.42%, H,5.18%, N, 5.76%；计算值：C:44.31%, H,5.14 %, N,5.55%；IR:3487, 3049, 2957, 2929，2872, 1642, 1609, 1572, 1509, 1480, 1464, 1416, 1379, 1331, 1288, 1246, 1178, 1141, 1123, 1099, 1045, 1018, 959, 933, 899, 854, 804, 770, 722, 693, 438;
配合物(I)晶体数据如下：
经验式 C36H50Cl4 N4O5 Pd2
分子量 973.40
温度 133(2) K
波长 0.71073Å
晶系， 空间群 单斜晶系, P2(1)
晶胞参数 a = 11.4699(8) Å α = 90 °.
b = 13.8149(9)Å β = 92.0580(10)°
c = 13.0964(9) Å γ = 90 °.
体积 2073.9（2）A^3
电荷密度 2, 1.559Mg/m^3
吸收 校正参数 1.169 mm^-1
单胞内的电子数目 988
晶体大小 0.176x 0.134x 0.112 mm
Theta 角的范围 1.777 to 26.000
HKL的指标收集范围 -14<=h<=14, -14<=k<17, -16<=l<=16
收集/独立衍射数据 15263/ 6933 [R(int) = 0.0323]
theta = 30.5的数据完整度 99.9%
吸收校正的方法 多层扫描
最大最小的透过率 0.7456 and 0.6960
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 6933/27/468
精修使用的方法 1.025
衍射点的一致性因子 R1 = 0.0324，wR2= 0.0753
可观察衍射的吻合因子 R1 = 0.0386, wR2 = 0.0785
绝对构型参数 -0.06（2）
差值傅里叶图上的最大峰顶和峰谷 0.863 and -0.607e.A^-3
晶体典型的键长数据：
Pd(1)-N(1) 2.005(6)
Pd(1)-N(4) 2.013(5)
Pd(1)-Cl(1) 2.2905(16)
Pd(1)-Cl(2) 2.2914(18)
Pd(2)-N(3) 2.013(5)
Pd(2)-N(2) 2.014(4)
Pd(2)-Cl(3) 2.2903(16)
Pd(2)-Cl(4) 2.2969(17)
晶体典型的键角数据：
N(1)-Pd(1)-N(4) 175.4(2)
N(1)-Pd(1)-Cl(1) 92.0(2)
N(4)-Pd(1)-Cl(1) 88.49(15)
N(1)-Pd(1)-Cl(2) 87.0(2)
N(4)-Pd(1)-Cl(2) 92.55(15)
Cl(1)-Pd(1)-Cl(2) 178.71(8)
N(3)-Pd(2)-N(2) 173.7(2)
N(3)-Pd(2)-Cl(3) 87.10(15)
N(2)-Pd(2)-Cl(3) 91.30(15)
N(3)-Pd(2)-Cl(4) 92.49(15)
N(2)-Pd(2)-Cl(4) 89.30(15)
Cl(3)-Pd(2)-Cl(4) 178.16(8)
C(1)-N(1)-C(3) 108.7(6)
C(1)-N(1)-Pd(1) 133.5(5)
C(3)-N(1)-Pd(1) 117.4(5)
C(13)-N(2)-C(15) 109.4(5)
C(13)-N(2)-Pd(2) 130.5(5)
C(15)-N(2)-Pd(2) 120.0(4)
C(19)-N(3)-C(21) 109.3(5)
C(19)-N(3)-Pd(2) 133.3(5)
C(21)-N(3)-Pd(2) 117.3(4)
C(31)-N(4)-C(33) 107.6(5)
C(31)-N(4)-Pd(1) 132.6(5)
C(33)-N(4)-Pd(1) 119.6(4)
C(1)-O(1)-C(2) 106.0(7)
C(13)-O(2)-C(14) 106.8(5)
C(19)-O(3)-C(20) 106.7(5)
C(31)-O(4)-C(32) 107.2(5)
（二）、亨利反应应用
1.E- β - 硝基苯乙烯的制备
取0.10mmol配合物(I)（催化用量为10％）于25mL的小烧瓶中，加入2毫升的四氢呋喃溶液，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72小时，用石油醚/二氯甲烷淋洗，进行柱层析, 产率 67.1 %. 1HNMR (300MHz, CDCl3), 8.00 (d, J=23Hz, 1H), 7.47～7.63 (m, 6H)。
（三）、腈硅化反应应用
2- 苯基 -2- （三甲硅氧基）乙腈的制备
0.10mmol化合物I, 苯甲醛0.1mL, TMSCN 0.3 ml (3.3mmol) 相继在20~30˚C下加入，72h 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：80.1%， 1HNMR (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)。
（3）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72小时后，进行核磁分析，转化率：36 %; 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)

1.一种手性双噁唑啉钯配合物，其化学式如下：
（Ⅰ）。
2.权利要求1所述的手性噁唑啉配合物(I)，在133（2）k温度下，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（λ=0.71073 Å）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,空间群 P2(1)，晶胞参数：a = 11.4699(7)Å，α = 90 °；b = 13.8149(9) Å, β = 92.0580（10）°; c = 13.0964(9) Å, γ= 90 °。
3.权利要求1所述的配合物(I)的合成方法，包括反应、分离和纯化，其特征由1，4-二氰基苯39.2mmol和L-缬氨醇16.2075g在无水无氧条件下和催化剂无水ZnCl2（26.4 mol%）于氯苯溶剂中回流反应60小时，然后分离、纯化，反应结束后脱去氯苯，将粗产品用石油醚/ 二氯甲烷(4:1)柱层析,得白色噁唑啉晶体,再按照噁唑啉与氯化钯摩尔比0.7:1，以氯苯为溶剂反应，用三氯甲烷、乙醇及正己烷进行重结晶，得红褐色双噁唑啉氯化钯配合物单晶。
4.该手性配合物在苯甲醛的亨利反应、腈硅化反应及Baylis-Hillman反应中显示一定的催化性能，其转化率分别达67.1%，80.1%, 36.2%。
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CN106800576A (zh) * 2017-01-19 2017-06-06 合肥祥晨化工有限公司 一种手性铂配合物晶体的制备及合成方法
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CN106800576A (zh) * 2017-01-19 2017-06-06 合肥祥晨化工有限公司 一种手性铂配合物晶体的制备及合成方法
CN110314165A (zh) * 2019-07-16 2019-10-11 合肥工业大学 一种手性噁唑啉钯配合物晶体的用途
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CN114621295B (zh) * 2022-03-23 2023-08-22 合肥工业大学智能制造技术研究院 一种手性噁唑啉钯配合物晶体及用途
CN114656417A (zh) * 2022-04-08 2022-06-24 合肥工业大学智能制造技术研究院 一种手性噁唑啉的合成方法及用途
CN114656417B (zh) * 2022-04-08 2023-10-13 合肥工业大学智能制造技术研究院 一种手性噁唑啉的合成方法及用途

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