CN111992254A - 脱质子苯基桥连β-酮亚胺锂配合物在氰硅化反应中的应用 - Google Patents
脱质子苯基桥连β-酮亚胺锂配合物在氰硅化反应中的应用 Download PDFInfo
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Abstract
本发明公开了脱质子苯基桥连β‑酮亚胺锂配合物在氰硅化反应中的应用,在该配合物中,每个β‑酮亚胺单元都是双负离子,而双负离子β‑酮亚胺基是一类活泼性很高的基团,例如可以和含有活泼氢的小分子以及不饱和键有机小分子反应。同时,该配合物也可以作为进一步合成双负离子β‑酮亚胺稀土金属配合物的前体。将该配合物应用于醛的氰硅化反应中,反应温度为室温,很少反应时间即可以实现醛和TMSCN的高效还原。
Description
技术领域
本发明涉及一种锂配合物及其在有机合成领域中的应用,具体涉及一种脱质子β-酮亚胺锂配合物、其制备方法及其在醛的氰硅化反应中的应用。
背景技术
在有机化学中,氰基硅烷化反应是最基本的碳-碳键形成反应之一,生成的产物在工业上是很有价值的底物和重要的中间体,因为它们可以进一步转化为许多有价值的有机化合物,例如α-羟基酸,α-氨基酸,β-氨基醇等。
1832年,Winkler首次报道了通过HCN作为氰化物来源制备氰醇,但是由于HCN具有很高的毒性并且后处理比较困难,于是,随后出现了大量危害较小且易于控制的替代氰化剂,到目前为止,三甲基氰硅烷(TMSCN)是最常用的氰化试剂,可以将其转化为氰醇三甲基甲硅烷基醚。近些年,化学工作者们开发出各类催化剂,应用于催化羰基化合物与TMSCN的氰硅化反应,与过渡金属催化剂对羰基氰基硅烷化的广泛研究相比,主族金属催化例如Al,Bi和Ca等催化羰基化合物和TMSCN的氰基硅烷化直到最近才引起人们越来越多的关注,特别是对于醛的氰硅化。然而,迄今为止,关于主族金属催化酮的氰硅化的报道比较少,2018年,Sen课题组和马猛涛课题组分别报道了关于有机锂化合物和有机镁化合物催化醛酮的氰硅化反应,在温和的反应条件下,以较低的催化剂用量可以实现醛酮的高效氰硅化,但这些催化剂合成比较困难,需要溶剂的使用,并且有的催化剂只对醛有很好的催化效果,酮的催化效果很差,底物试用范围受到限制。目前文献上报道的关于合成本发明所报道的醛酮的氰硅化的催化体系主要包括主族金属催化[(a)V. S. V. S. N. Swamy, M. K. Bisai,T. Das, S. S. Sen, Chem. Commun. 2017, 53, 6910; (b) M. K. Bisai, T. Das, K.Vanka, S. S. Sen, Chem. Commun. 2018, 54, 6843; (c) W. Wang, M. Luo, J. Li,S.A. Pullarkat, M. Ma, Chem. Commun. 2018, 54, 3042; (d) J. Li, T.Yu, M. Luo,Q. Xiao, W. Yao, L. Xu, M. Ma, J. Organomet. Chem.2018, 874, 83; (e) S.Yadav, R. Dixit, K. Vanka, S. S. Sen, Chem. Eur J. 2017, 24, 1269.]、过渡金属催化[(a)M. K. Sharma, D. Singh, P. Mahawar, R. Yadav, S. Nagendran, Dalton Trans.2018, 47, 5943; (b) A. V. Gurbanov, G. Mahmoudi, M. F. C. Guedes daSilva, F. I. Zubkov, K. T. Mahmudov, A. J. L. Pombeiro, Inorg. Chim. Acta.2018, 471, 130; (c) Z. Zhang, Z. Wang, R. Zhang, K. Ding, Angew. Chem. Int. Ed.2010, 49, 6746.] 以及稀土金属催化 [ (a) H. An, Y. Zhang, Y. Hou, T. Hu, W.Yang, S. Chang, J. Zhang, Dalton Trans. 2018, 47, 9079; (b) F. Wang, Y. Wei,S. Wang, X. Zhu, S. Zhou, G. Yang, X. Gu, G. Zhang, X. Mu, Organometallics,2015, 34, 86.]。
β-酮亚胺作为一类重要的非茂基配体,具有易于合成,其电荷及空间效应可通过α位及β位的取代基的改变得以方便调控,以及可以通过多种配位方式与金属配位,从而形成结构多样性的金属配合物等特点。然而,与β-二亚胺阴离子配体在有机金属化学上的研究相比,β-酮亚胺阴离子配体的应用研究却较少。已有的报道集中在单负离子β-酮亚胺为骨架的配合物上。关于双负离子β-酮亚胺配体的配合物迄今为止没有报道。
发明内容
本发明的发明目的是提供脱质子苯基桥连β-酮亚胺锂配合物在醛氰硅化反应中的应用,为一种新的羰基化合物氰硅化反应方法,有好的底物适用范围。
为达到上述目的,本发明采用的技术方案是:
脱质子苯基桥连β-酮亚胺锂配合物在氰硅化反应中的应用,所述氰硅化反应以醛、硅烷为反应底物。
本发明还公开了一种醛氰硅化反应的方法,包括以下步骤,以脱质子苯基桥连β-酮亚胺锂配合物为催化剂,以醛和硅烷为原料,反应完成氰硅化反应。
本发明中,所述脱质子苯基桥连β-酮亚胺锂配合物的化学结构式如下:
上述技术方案中,氰硅化反应的温度为室温,时间为10~18min,优选15min,然后接触空气终止反应。
上述技术方案中,所述硅烷为三甲基氰硅烷(TMSCN);所述醛为苯甲醛、对氟苯甲醛、邻硝基苯甲醛,对甲基苯甲醛,肉桂醛。
上述技术方案中,所述催化剂脱质子苯基桥连β-酮亚胺锂配合物的用量为醛的摩尔量的0.05%;所述硅烷和醛的摩尔比为1.1:1。
本发明中,上述脱质子苯基桥连β-酮亚胺锂配合物的制备方法包括以下步骤,将小分子有机锂溶液与配体溶液混合,然后反应,得到催化剂脱质子苯基桥连β-酮亚胺锂配合物;所述配体的化学结构式如下:
本发明,氰硅化反应在惰性气氛下进行,惰性气氛优选为氮气。
本发明所述氰硅化反应在无溶剂条件下进行。本发明氰硅化反应的反应示意如下:
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明利用首次公开的脱质子苯基桥连β-酮亚胺锂配合物催化醛和TMSCN的氰硅化反应,从而开发出一类高效的催化氰硅化反应的方法,其结构简单,合成容易,可以在室温条件下高活性的催化醛和TMSCN的氰硅化反应,催化剂用量仅为醛摩尔量的0.05%,反应可达99%以上的收率,与已有的催化体系相比,降低了催化剂用量,温度温和,并且产率很高。
附图说明
图1为实施例一产物的核磁图;
图2为实施例三产物的核磁图。
具体实施方式
本发明涉及的原料都是市售产品,在本发明制备方法下,具体的操作步骤以及测试方法都是本领域常规方法;β-酮亚胺配体的合成在空气中进行;脱质子苯基桥连β-酮亚胺锂配合物的合成在氩气保护下进行;氰硅化反应产物可直接使用或者进行常规提纯。
核磁收率计算:
核磁收率 = 产物特征峰面积/原料醛特征峰面积。
合成例
邻苯基桥连β-酮亚胺配体(LphH2)的合成
在三颈瓶中加入150 ml无水乙醇,10.8 g间苯二胺 (100 mmol),20.5 mL乙酰丙酮(200 mmol),催化量对甲苯磺酸,加热回流24小时,得到红棕色液体及淡黄色固体混合物,抽滤,固体用无水乙醇重结晶,得淡黄色针状晶体24.5 g,得率90%,为配体LphH2。1H NMR(400 MHz, CDCl3):δ12.47 (2H, s, NH),7.32-7.27 (1H, m, ArH), 6.94-6.91 (2H, m,ArH), 6.86 (1H, s, ArH), 5.21 (2H, s, CH=C(CH3)N),2.10 (6H, s, CH 3),2.01 (6H,s, CH 3)。13C NMR (101 MHz, CDCl3): δ 196.54 (COCH3), 159.62 (C=CH), 139.63(ArC), 129.71 (ArC), 121.45 (ArC), 120.43 (ArC), 98.20 (=CH), 29.25 (CH3),19.94 (CH3)。HRMS (ESI-MS) calcd. for C16H20N2O2 [M+H]+: 273.1558, found:273.1633。
脱质子苯基桥连β-酮亚胺锂配合物[Lph’Li4(THF)4]2的合成
LphH2 + 4 n-BuLi → 1/2 [Lph’Li4(THF)4]2 + 4 n-BuH ↑
在冰浴条件下,将正丁基锂的己烷溶液(19.40 mmol, 2.5 M)加入到LphH2 (4.85mmol)的四氢呋喃溶液中,溶液由淡黄色清液逐渐变为浅桔红色浊液,1分钟加完之后,在室温下反应12 h;反应结束后,对反应液加热至100oC使其能够变成桔红色清液,清液浓缩至出现浑浊,离心,将上层清液继续浓缩,有大量碎晶产生,加热溶解,然后自然冷却至室温,封瓶,室温下静置50分钟,析出大量的淡黄色晶体[Lph’Li4(THF)4]2 {Lph’ = C6H4[NC(CH3)=CHCO=CH2]2},常规分离干燥,得到产物2.22 g,产率78%。熔点:194.6-196.7 oC。1H NMR(400 MHz, d8-THF):δ 7.29 (s, 1H, ArH), 6.95 (t, J = 7.7 Hz, 3H, ArH), 6.31(d, J = 2.0 Hz, 2H, =CH 2), 6.29 (d, J = 2.0 Hz, 2H, =CH 2), 5.18 (t, J = 1.9Hz, 2H, CH=C(CH3)N), 1.66 (s, 6H, CH 3). IR (KBr, cm-1): 3677, 3189, 2972,1567, 1501, 1470, 1413, 1379, 1358, 1311, 1277, 1239, 1194, 1153, 1065, 1021,968, 926, 886, 744, 697, 643。
配合物[Lph’Li4(THF)4]2:
从配合物[Lph’Li4(THF)4]2的单晶结构和晶体学参数中看到,该配合物是一个具有对称结构的β-酮亚胺锂配合物,溶剂THF分别络合在不同的Li原子上。Li (1) 原子周围没有配位溶剂,Li (2) 原子周围络合了两个THF分子,Li (3) 原子和Li (4) 原子周围分别络合了一个THF分子。它属于三斜晶系,P1空间群。
配合物1的晶体结构参数
实施例一:[Lph’Li4(THF)4]2 催化苯甲醛和TMSCN的还原反应
在氮气氛围下,向经过脱水脱氧处理后的反应瓶中加入催化剂0.6 mg(0.0005mmol,0.05%),用移液枪依次加入苯甲醛 (101.6 μL, 1.0 mmol),TMSCN (137.6 μL, 1.1mmol), 在室温反应15 min后,用滴管吸取一滴于核磁管中,加入CDCl3配成溶液。经计算1H谱产率为99%。产物的核磁数据: 1H NMR (400 MHz, CDCl3) δ7.41-7.29 (m, 5H, ArH),5.42 (s, 1H, CHOSi(CH3)3), 0.15 (s, 9H, Si(CH 3)3),图谱见图1。
实施例二:[Lph’Li4(THF)4]2催化对氟苯甲醛和TMSCN的还原反应
在氮气氛围下,向经过脱水脱氧处理后的反应瓶中加入催化剂0.6 mg(0.0005mmol),用移液枪依次加入对氟苯甲醛 (107.2 μL, 1.0 mmol),TMSCN (137.6 μL, 1.1 mmol),在室温反应15 min后,用滴管吸取一滴于核磁管中,加入CDCl3配成溶液。经计算1H谱产率为99%。产物的核磁数据: 1H NMR (400 MHz, CDCl3) δ7.48-7.44 (m, 2H, ArH), 7.12-7.08(m, 2H, ArH), 5.48 (s, 1H, CHOSi(CH3)3), 0.23 (s, 9H, Si(CH 3)3)。
实施例三:[Lph’Li4(THF)4]2催化邻硝基苯甲醛和TMSCN的还原反应
在氮气氛围下,向经过脱水脱氧处理后的反应瓶中加入催化剂0.6 mg(0.0005mmol),邻硝基苯甲醛(151.1mg, 1.0 mmol),用移液枪加入TMSCN (137.6 μL, 1.1 mmol),在室温反应15 min后,用滴管吸取一滴于核磁管中,加入CDCl3配成溶液。经计算1H谱产率为99%。1HNMR (400 MHz, CDCl3) δ8.11 (d, 3 J H-H = 8.2 Hz, 1H, ArH), 7.99 (d, 3 J H-H = 7.7Hz, 1H, ArH), 7.75 (t, 3 J H-H = 8.2 Hz, 1H, ArH), 7.57(t, 3 J H-H = 8.4 Hz, 1H,ArH), 6.20 (s, 1H, CHOSi(CH3)3), 0.26 (s, 9H, Si(CH 3)3) ,图谱见图2。
实施例四:[Lph’Li4(THF)4]2催化对甲基苯甲醛和TMSCN的还原反应
在氮气氛围下,向经过脱水脱氧处理后的反应瓶中加入催化剂0.6 mg(0.0005mmol),用移液枪依次加入对甲基苯甲醛 (117.9 μL, 1.0 mmol),TMSCN (137.6 μL, 1.1 mmol),在室温反应15 min后,用滴管吸取一滴于核磁管中,加入CDCl3配成溶液。经计算1H谱产率为99%。产物的核磁数据: 1H NMR (400 MHz, CDCl3) δ7.28 (d, 3 J H-H = 8.1 Hz, 2H, ArH),7.13 (d, 3 J H-H = 7.9 Hz, 2H, ArH), 5.38 (s, 1H, CHOSi(CH3)3), 2.28 (s, 3H, Ar-Me) , 0.14 (s, 9H, Si(CH 3)3)。
实施例五:[Lph’Li4(THF)4]2催化肉桂醛和TMSCN的还原反应
在氮气氛围下,向经过脱水脱氧处理后的反应瓶中加入催化剂0.6 mg(0.0005mmol),用移液枪依次加入肉桂醛 (125.8 μL, 1.0 mmol),TMSCN (137.6 μL, 1.1 mmol),在室温反应15 min后,用滴管吸取一滴于核磁管中,加入CDCl3配成溶液。经计算1H谱产率为98%。产物的核磁数据: 1H NMR (400 MHz, CDCl3) δ7.33-7.22 (m, 5H, ArH), 6.73 (d, 3 J H-H =15.8 Hz, 1H, PhCHCH), 6.10 (dd, 3 J H, H = 15.8, 6.0 Hz, 1H, PhCHCH), 5.03 (d,3 J H, H = 7.1 Hz, 1H, CHOSi(CH3)3), 0.18 (s, 9H, Si(CH 3)3)。
本发明通过邻苯基桥连的β-酮亚胺配体LphH2与四倍当量的正丁基锂己烷溶液在THF中反应时,可以方便地得到脱质子的邻苯基桥连的β-酮亚胺锂配合物,在该配合物中,每个β-酮亚胺单元都是双负离子,而双负离子β-酮亚胺基是一类活泼性很高的基团,例如可以和含有活泼氢的小分子以及不饱和键有机小分子反应。同时,该配合物也可以作为进一步合成双负离子β-酮亚胺稀土金属配合物的前体。将该配合物应用于醛的氰硅化反应中,当以0.05 mol% 脱质子苯基桥连β-酮亚胺锂配合物为催化剂,反应温度为室温,反应时间为15 min,可以实现醛和TMSCN的高效还原。
Claims (9)
2.根据权利要求1所述脱质子苯基桥连β-酮亚胺锂配合物在醛氰硅化反应中的应用,其特征在于,所述氰硅化反应以醛、硅烷为反应底物。
3.根据权利要求2所述脱质子苯基桥连β-酮亚胺锂配合物在醛氰硅化反应中的应用,其特征在于,醛为苯甲醛、对氟苯甲醛、邻硝基苯甲醛、对甲基苯甲醛、肉桂醛。
4.根据权利要求2所述脱质子苯基桥连β-酮亚胺锂配合物在醛氰硅化反应中的应用,其特征在于,硅烷为三甲基氰硅烷。
5.根据权利要求1所述脱质子苯基桥连β-酮亚胺锂配合物在醛氰硅化反应中的应用,其特征在于,氰硅化反应在惰性气氛下进行。
6.一种醛氰硅化反应的方法,包括以下步骤,以权利要求1所述脱质子苯基桥连β-酮亚胺锂配合物为催化剂,以醛和硅烷为原料,反应完成氰硅化反应。
7.根据权利要求6所述醛氰硅化反应的方法,其特征在于,氰硅化反应的温度为室温,时间为10~18min。
8.根据权利要求6所述醛氰硅化反应的方法,其特征在于,催化剂的用量为醛摩尔量的0.05%。
9.根据权利要求6所述醛氰硅化反应的方法,其特征在于,硅烷和醛的摩尔比为1.1:1。
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