CN114591357B - B(9)-胺基邻碳硼烷类化合物的合成方法 - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种B(9)‑胺基邻碳硼烷类化合物的合成方法,属于有机合成技术领域。以邻碳硼烷类化合物1和苯甲酸取代胺类化合物2为原料,在钯催化剂和银盐添加剂存在下,有机溶剂中反应,得到B(9)‑胺基邻碳硼烷类化合物3。本发明通过邻碳硼烷类化合物和苯甲酸取代的胺类化合物之间的偶联反应,一步即可得到B(9)‑胺基邻碳硼烷类化合物;该方法具有官能团耐受性好、反应条件温和、区域选择性高等优点,具有潜在的应用前景。
Description
技术领域
本发明属于元素化学技术领域,具体涉及一种B(9)-胺基邻碳硼烷类化合物的合成方法。
背景技术
碳硼烷及其衍生物由于其独特的三维立体结构、低毒性以及良好的热稳定性和化学稳定性等特点,已经被应用于众多领域,如生物医学、光化学、超分子和配位化学、材料化学等。近年来,碳硼烷在核医学领域的发展呈多样化趋势,不仅在传统的BNCT领域有着丰富多彩的应用,而且在放射性分子成像和治疗等领域也发挥着重要作用。2020年8月我国首台硼中子俘获治疗实验装置在中科院高能物理所东莞分部研制成功,急需含硼药物与之配合,充分发挥这种靶向加放疗治疗手段造福癌症病人。碳硼烷衍生物作为高硼含量化合物,是潜在BNCT药物。因此,对碳硼烷进行选择性官能团化,从而得到各种各样的功能性分子,成为了近年来的研究热点之一。
由于氨基取代碳硼烷在医学、配位化学及金属催化领域的重要应用,近年来得到了硼化学家们广泛关注,并取得了重要进展。但目前碳硼烷的胺基化主要发生在B(4)或B(3)位,B(9)位直接胺化,还没有被报道。
因此,研究并开发从简单易得原料出发、通过简便途径和过程合成B(9)-胺基邻碳硼烷类化合物的新方法,具有十分重要的理论意义和应用前景。
发明内容
本发明解决的技术问题是提供了一种B(9)-胺基邻碳硼烷类化合物的合成方法,该方法通过钯催化的B(9)-H键活化,合成了B(9)-胺基邻碳硼烷类化合物,具有原料易得、官能团耐受性好、反应条件温和、区域选择性高、原子经济性好等优点,具有潜在的应用前景。
本发明为解决上述技术问题,采用如下技术方案,一种B(9)-胺基邻碳硼烷类化合物的合成方法,包括如下操作:以邻碳硼烷类化合物1和苯甲酸取代胺类化合物2为原料,在钯催化剂和添加剂存在下,有机溶剂中反应,得到B(9)-胺基邻碳硼烷类化合物3。
反应方程式为:
其中:R独立选自氢、C1-10烷基、苄基、氯甲基、C1-C4烷基酯、取代苯基、噻吩基、三甲基硅基,取代苯基中取代基为氢、硝基、三氟甲基、卤素、C1-C4烷基、C1-C4烷氧基中的一种或多种;或者相邻两个R基组成5-7元环烷基、苯基、四乙基苯基、苯并环烷基;R'为氢、卤素、C1-C4烷基;R1,R2分别独立选自氢、C1-C4烷基、二氟乙基、3-[4-三氟甲基苯氧基]苯丙基、甲氧乙基、C3-C7环烷基;或者R1,R2与N组成吗啉、甲基吗啉。
进一步地,在上述技术方案中,所述催化剂为醋酸钯[Pd(OAc)2]、二水合硝酸钯[Pd(NO3)2 .2H2O]或三氟醋酸钯[Pd(TFA)2]。
进一步地,在上述技术方案中,所述添加剂为银盐添加剂;银盐添加剂为醋酸银、六氟锑酸银或碳酸银。
进一步地,在上述技术方案中,所述有机溶剂为六氟异丙醇或三氟乙酸。
进一步地,在上述技术方案中,所述邻碳硼烷类化合物1、氮氧化合物2、钯催化剂与银盐添加剂摩尔比为1:1.2-2.5:0.1:1.5-3。
进一步地,在上述技术方案中,反应温度为0-80℃。
发明有益效果:
本发明具有以下优点:(1)合成过程简单,反应条件温和,无需惰性气体保护;(2)底物适用范围广和官能团耐受性好;(3)区域选择性高。
说明书附图
图1为实施例3中化合物3ea的X-射线单晶衍射图;
图2为实施例3中化合物3ha的X-射线单晶衍射图;
图3为实施例5中化合物3oa的X-射线单晶衍射图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
向15mL反应管中,依次加入化合物1a、化合物2a、催化剂、银盐添加剂和溶剂,在空气条件下将反应管密封,室温反应。待反应结束后,加入饱和碳酸氢钠溶液淬灭反应,乙酸乙酯(10mL×3)萃取,合并有机相,饱和氯化钠水溶液洗涤,无水硫酸钠干燥,抽滤,旋干,硅胶柱分离(二氯甲烷:乙酸乙酯=8:1)得到白色固体产物3aa。
通过改变反应溶剂、催化剂、银盐添加剂等反应条件,结果如下:
表1不同条件下3aa的合成
序号 | 催化剂(10mol%) | 银盐添加剂(1.5当量) | 溶剂 | 产率(%) |
1 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | --- | HFIP | 58 |
2 | <![CDATA[Pd(NO<sub>3</sub>)<sub>2</sub>·2H<sub>2</sub>O]]> | --- | HFIP | 32 |
3 | <![CDATA[Pd(TFA)<sub>2</sub>]]> | --- | HFIP | trace |
4 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | --- | DCE | 0 |
5 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | --- | <![CDATA[CH<sub>3</sub>CN]]> | 0 |
6 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | --- | <![CDATA[CF<sub>3</sub>COOH]]> | 6 |
7 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | --- | HOAc | 0 |
8 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | AgOAc | HFIP | 85 |
9 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | <![CDATA[AgSbF<sub>6</sub>]]> | HFIP | 72 |
10 | <![CDATA[Pd(OAc)<sub>2</sub>]]> | <![CDATA[Ag<sub>2</sub>CO<sub>3</sub>]]> | HFIP | 57 |
实施例2
向15mL反应管中,依次加入化合物1a(51.6mg,0.3mmol)、化合物2a(93.2mg,0.45mmol)、醋酸钯(6.7mg,0.03mmol)、醋酸银(76.8mg,0.45mmol)和六氟异丙醇(3mL),在空气条件下将反应管密封,室温反应36小时。待反应结束后,加入饱和碳酸氢钠溶液淬灭反应,乙酸乙酯(10mL×3)萃取,合并有机相,饱和氯化钠水溶液洗涤,无水硫酸钠干燥,抽滤,旋干,硅胶柱分离(二氯甲烷:乙酸乙酯=8:1)得到白色固体产物3aa(66mg,85%)。1H NMR(600MHz,CDCl3)δ:3.56(t,J=4.5Hz,4H),2.62(t,J=4.5Hz,4H),2.08(s,3H),2.00(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:67.9,67.8,59.6,51.0,23.7,21.3.11B{1H}NMR(193MHz,CDCl3)δ:11.3(1B),-7.3(1B),-10.9(8B).HRMS(ESI-TOF)m/z calcd for C8B10H24NO[M+H]+:258.2860.Found:258.2850.
实施例3
依照实施例2的方法,反应条件为:1(0.3mmol),2(0.45mmol),Pd(OAc)2(0.03mmol),AgOAc(0.45mmol),六氟异丙醇(3mL),空气氛围下室温反应36h;通过改变反应物1和反应物2,合成出各种B(9)-胺基邻碳硼烷类化合物3。
具体结果如下:
产物表征数据如下:
3ba:white solid,(81mg,83%),1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.5Hz,4H),2.67(t,J=4.8Hz,4H),2.29(q,J=7.6Hz,2H),2.21(q,J=7.6Hz,2H),1.18(t,J=7.6Hz,3H),1.14(t,J=7.6Hz,3H).13C{1H}NMR(151MHz,CDCl3)δ:75.3,67.8,66.9,51.1,28.8,26.7,14.5,13.9.11B{1H}NMR(193MHz,CDCl3)δ:11.5,-7.0,-11.8,-12.8,-13.6.HRMS(ESI-TOF):m/z calcd for C10B10H28NO[M+H]+:286.3174.Found:286.3169.
3ca:white solid,(80mg,78%),1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.2Hz,4H),2.67(t,J=4.5Hz,4H),2.20-2.15(m,2H),2.12-2.07(m,2H),1.56-1.44(m,4H),1.33(dt,J=20.4,7.4Hz,4H),0.92(td,J=7.3,3.7Hz,6H).13C{1H}NMR(151MHz,CDCl3)δ:74.8,67.6,65.1,51.2,35.1,33.0,32.2,31.6,22.5,22.4,13.7.11B{1H}NMR(193MHz,CDCl3)δ:11.5(1B),-7.0(1B),-12.6(8B).HRMS(ESI-TOF):m/z calcd for C14B10H36NO[M+H]+:342.3802.Found:342.3795.
3da:white solid,(103mg,76%),1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.5Hz,4H),2.67(t,J=4.8Hz,4H),2.19-2.14(m,2H),2.11-2.06(m,2H),1.57-1.45(m,4H),1.34-1.20(m,21H),0.88(t,J=7.0Hz,6H).13C{1H}NMR(151MHz,CDCl3)δ:74.6,67.8,66.1,51.1,35.4,33.3,31.7,30.2,29.5,29.3,29.2,29.1,29.1,22.6,14.1.11B{1H}NMR(193MHz,CDCl3)δ:11.5(1B),-6.9(1B),-11.7(8B).HRMS(ESI-TOF):m/z calcd for C22B10H52NO[M+H]+:454.5057.Found:454.5048.
3ea:white solid,(78mg,83%),1H NMR(600MHz,CDCl3)δ:3.58(t,J=4.8Hz,4H),2.67(t,J=4.8Hz,4H),2.34(hept,J=6.6Hz,1H),2.28(hept,J=6.6Hz,1H),1.23(t,J=9.0Hz,6H),1.18(d,J=6.9Hz,6H).13C{1H}NMR(151MHz,CDCl3)δ:83.6,74.5,67.9,51.1,30.7,29.3,24.8,24.2.11B{1H}NMR(193MHz,CDCl3)δ:11.8(1B),-6.6(1B),-10.8(2B),-14.2(6B).HRMS(ESI-TOF):m/z calcd for C12B10H32NO[M+H]+:314.3488.Found:314.3484.
3fa:white solid,(66mg,78%),1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.5Hz,4H),2.64(t,J=4.5Hz,4H),2.57-2.53(m,2H),2.51-2.46(m,2H),2.46-2.41(m,2H).13C{1H}NMR(151MHz,CDCl3)δ:79.3,72.1,67.8,51.2,34.5,32.9,32.9.11B{1H}NMR(193MHz,CDCl3)δ:10.2(1B),-8.8(3B),-11.0(2B),-13.8(4B).HRMS(ESI-TOF):m/z calcd for C9B10H24NO[M+H]+:270.2860.Found:270.2875.
3ga:white solid,(71mg,84%),1H NMR(600MHz,CDCl3)δ:3.58(t,J=4.5Hz,4H),2.64(t,J=4.8Hz,4H),2.50(t,J=6.1Hz,2H),2.38(t,J=6.0Hz,2H),1.62-1.54(m,4H).13C{1H}NMR(151MHz,CDCl3)δ:67.8,59.5,51.1,33.1,31.1,20.0,19.4.11B{1H}NMR(193MHz,CDCl3)δ:10.6(1B),-7.7(1B),-11.9(8B).HRMS(ESI-TOF):m/z calcd forC10B10H26NO[M+H]+:284.3017.Found:284.3014.
3ha:white solid,(48mg,59%),1H NMR(600MHz,CDCl3)δ:3.56(t,J=4.5Hz,4H),2.70(t,J=4.8Hz,4H),2.05(s,3H),1.99(s,3H),0.19(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:68.2,63.1,59.0,50.7,23.0,21.5.11B{1H}NMR(193MHz,CDCl3)δ:10.8(1B),4.4(1B),-11.7(8B).HRMS(ESI-TOF):m/z calcd for C9B10H26NO[M+H]+:272.3017.Found:272.3026.
3ia:white solid,(55mg,80%),1H NMR(600MHz,CDCl3)δ:3.60(t,J=4.8Hz,4H),3.34(d,J=9.0Hz,2H),2.69(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:67.8,50.8,49.0,30.9.11B{1H}NMR(193MHz,CDCl3)δ:13.0(1B),-5.0(1B),-10.5(2B),-16.4(6B).HRMS(ESI-TOF):m/z calcd for C6B10H20NO[M+H]+:230.2546.Found:230.2548.
3ab:white solid,(67mg,83%),1H NMR(600MHz,CDCl3)δ:3.64(dd,J=10.6,2.5Hz,1H),3.54(dd,J=10.6,2.8Hz,1H),3.46(d,J=10.5Hz,1H),3.38(td,J=11.2,3.0Hz,1H),3.11-3.04(m,1H),2.97(d,J=4.8Hz,1H),2.53(d,J=12.8Hz,1H),2.07(s,4H),1.99(s,3H),1.13(d,J=6.7Hz,3H).13C{1H}NMR(151MHz,CDCl3)δ:72.3,68.3,67.2,57.6,51.1,44.1,23.8,21.2,13.3.11B{1H}NMR(193MHz,CDCl3)δ:10.8(1B),-7.5(1B),-11.4(8B).HRMS(ESI-TOF):m/z calcd for C9B10H26NO[M+H]+:272.3017.Found:272.3011.
3ac:white solid,(69mg,85%),1H NMR(600MHz,CDCl3)δ:3.64(dd,J=10.6,2.8Hz,1H),3.55(dd,J=10.6,3.0Hz,1H),3.46(d,J=10.5Hz,1H),3.42-3.34(m,1H),3.08(ddd,J=13.0,11.9,3.3Hz,1H),2.97(d,J=4.5Hz,1H),2.53(d,J=11.9Hz,1H),2.07(s,3H),1.99(s,3H),1.13(d,J=6.7Hz,3H).13C{1H}NMR(151MHz,CDCl3)δ:72.3,68.3,67.2,57.6,51.1,44.1,23.8,21.2,13.3.11B{1H}NMR(193MHz,CDCl3)δ:10.9(1B),-7.4(1B),-11.3(8B).HRMS(ESI-TOF):m/z calcd for C9B10H26NO[M+H]+:272.3017.Found:272.3013.
3ad:white solid,(102mg,87%),1H NMR(600MHz,CDCl3)δ:7.41(d,J=8.7Hz,2H),7.35-7.30(m,4H),7.26-7.24(m,1H),6.90(d,J=8.7Hz,2H),5.21(dd,J=8.8,3.9Hz,1H),2.87(ddd,J=51.7,12.1,6.2Hz,2H),2.05(m,9H),1.90(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:160.9,141.9,128.6,127.4,126.5(t,J=3.5Hz),125.8,124.5(t,J=271.8Hz),122.3(d,J=33.2Hz),115.8,78.2,67.5,58.0,51.7,40.3,37.2,29.7,23.6.11B{1H}NMR(193MHz,CDCl3)δ:11.7(1B),-7.2(1B),-11.3(8B).19FNMR(565MHz,CDCl3)δ:-61.44.HRMS(ESI-TOF):m/z calcd for C14B10H28NOF3[M+H]+:391.3128.Found:391.3122.
3ae:white solid,(55mg,71%),1H NMR(600MHz,CDCl3)δ:3.39(t,J=6.8Hz,2H),3.33(s,3H),2.88(d,J=6.7Hz,2H),2.48(s,3H),2.07(s,3H),1.99(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:76.8,71.2,67.5,58.7,57.9,54.5,41.1,23.8,21.2.11B{1H}NMR(193MHz,CDCl3)δ:11.6(1B),-7.3(1B),-11.2(8B).HRMS(ESI-TOF):m/z calcd forC8B10H26NO[M+H]+:260.3016.Found:260.3011.
3af:white solid,(77mg,85%),1H NMR(600MHz,CDCl3)δ:3.34-3.27(m,10H),2.92(t,J=7.0Hz,4H),2.05(s,3H),1.97(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:72.0,67.3,58.7,57.3,52.5,23.7,21.1.11B{1H}NMR(193MHz,CDCl3)δ:11.2(1B),-7.4(1B),-11.6(8B).HRMS(ESI-TOF):m/z calcd for C10B10H30NO2[M+H]+:304.3279.Found:304.3273.
实施例4
向15mL反应管中,依次加入化合物1j(89mg,0.3mmol)、化合物2a(93.2mg,0.45mmol)、醋酸钯(6.7mg,0.03mmol)、六氟磷酸银(114mg,0.45mmol)和六氟异丙醇(3mL),在空气条件下将反应管密封,70℃反应36小时。待反应结束后,加入饱和碳酸氢钠溶液淬灭反应,乙酸乙酯(10mL×3)萃取,合并有机相,饱和氯化钠水溶液洗涤,无水硫酸钠干燥,抽滤,旋干,硅胶柱分离(石油醚:乙酸乙酯=7:1)得到白色固体产物3ja(103mg,90%)。1HNMR(600MHz,CDCl3)δ:7.47(d,J=7.6Hz,2H),7.41(d,J=7.6Hz,2H),7.22(dd,J=10.7,4.0Hz,2H),7.16-7.11(m,4H),3.63(t,J=4.5Hz,4H),2.77(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:131.1,130.8,130.5,130.1,130.0,129.8,128.2,79.9,71.2,67.8,51.1.11B{1H}NMR(193MHz,CDCl3)δ:13.7(1B),-4.8(1B),-12.6(8B).HRMS(ESI-TOF):m/zcalcd for C18B10H27NO[M+H]+:382.3177.Found:382.3178.
实施例5
依照实施例4方法,反应条件为:1(0.3mmol),2a(0.45mmol),Pd(OAc)2(0.03mmol),AgPF6(0.45mmol),六氟异丙醇(3mL),空气氛围下70℃反应36h;通过改变反应物1,合成出各种B(9)-胺基邻碳硼烷类化合物3。
具体结果如下:
3ka:white solid,(98mg,80%),1H NMR(600MHz,CDCl3)δ:7.40-7.33(m,6H),7.26-7.20(m,4H),3.69(s,2H),3.62(s,2H),3.52(t,J=4.5Hz,4H),2.56(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:135.5,134.9,130.3,128.6,128.1,128.0,74.2,67.7,65.9,50.9,41.6,39.6.11B{1H}NMR(193MHz,CDCl3)δ:11.3(1B),-7.1(1B),-12.9(8B).HRMS(ESI-TOF):m/z calcd for C20B10H32NO[M+H]+:410.3491.Found:410.3483.
3la:white solid,(48mg,45%),1H NMR(600MHz,CDCl3)δ:7.23(dd,J=5.7,3.4Hz,2H),7.07(ddd,J=9.1,5.0,3.4Hz,2H),3.79(s,2H),3.67(s,2H),3.61(t,J=4.5Hz,4H),2.69(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:129.6,129.0,128.8,128.7,127.6,127.6,67.8,51.1,38.0,36.0.11B{1H}NMR(193MHz,CDCl3)δ:11.2(1B),-7.0(1B),-11.5(8B).HRMS(ESI-TOF):m/z calcd for C14B10H25NONa[M+Na]+:354.2838.Found:354.2840.
3ma:white solid,(101mg,82%),1H NMR(600MHz,CDCl3)δ:7.35(d,J=8.4Hz,2H),7.29(d,J=8.4Hz,2H),6.93(d,J=7.7Hz,4H),3.62(t,J=4.8Hz,4H),2.77(t,J=4.5Hz,4H),2.22(s,6H).13C{1H}NMR(151MHz,CDCl3)δ:140.3,140.2,131.0,130.4,128.9,128.2,127.1,80.3,71.5,67.8,51.1,20.9.11B{1H}NMR(193MHz,CDCl3)δ:13.4(1B),-5.0(1B),-12.6(8B).HRMS(ESI-TOF):m/z calcd for C20B10H32NO[M+H]+:410.3491.Found:410.3489.
3na:white solid,(34mg,22%),1H NMR(600MHz,CDCl3)δ:7.62(d,J=8.4Hz,2H),7.55(d,J=8.4Hz,2H),7.44(dd,J=8.4,1.8Hz,4H),3.62(t,J=4.5Hz,4H),2.77(t,J=4.8Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:134.1,133.4,132.4(q,J=33.0Hz),131.6(d,J=16.2Hz),130.9,130.1,128.4,123.2(q,J=272.3,3.4Hz),69.1,68.0,67.8,50.9.11B{1H}NMR(193MHz,CDCl3)δ:14.2(1B),-4.1(1B),-12.3(8B).19F NMR(565MHz,CDCl3)δ:-63.21,-63.20.HRMS(ESI-TOF):m/z calcd for C20B10H26NOF6[M+H]+:518.2926.Found:518.2925.
3oa:white solid,(99mg,79%),1H NMR(600MHz,CDCl3)δ:7.48-7.44(m,2H),7.42-7.37(m,2H),6.87-6.82(m,4H),3.61(t,J=4.5Hz,4H),2.75(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:164.4,162.8,133.2(d,J=8.8Hz),132.5(d,J=8.8Hz),126.8(d,J=3.3Hz),125.8(d,J=3.3Hz),115.5,115.4,79.1,70.2,67.8,51.0.11B{1H}NMR(193MHz,CDCl3)δ:13.8(1B),-4.6(1B),-12.4(8B).19F NMR(565MHz,CDCl3)δ:-109.59,-109.69.HRMS(ESI-TOF):m/z calcd for C18B10H26NOF2[M+H]+:418.2990.Found:418.2984.
3pa:white solid,(80mg,64%),1H NMR(600MHz,CDCl3)δ:7.28(dd,J=8.0,1.0Hz,1H),7.21(ddd,J=8.3,4.0,1.4Hz,2H),7.14(tdd,J=5.6,4.5,1.4Hz,3H),6.97(td,J=8.1,1.1Hz,2H),3.61(t,J=4.8Hz,4H),2.76(t,J=4.8Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:162.8(d,J=6.2Hz),161.2(d,J=6.4Hz),132.8(d,J=7.8Hz),131.9(d,J=8.2Hz),130.1-129.8(m),126.9(d,J=2.7Hz),126.2(d,J=2.4Hz),118.5,118.4,117.9,117.7,117.5(dd,J=20.9,1.6Hz),78.4,69.5,67.8,50.9.11B{1H}NMR(193MHz,CDCl3)δ:13.8(1B),-4.5(1B),-12.4(8B).19F NMR(565MHz,CDCl3)δ:-105.17,-106.07.HRMS(ESI-TOF):m/z calcd for C18B10H26N OF2[M+H]+:418.2990.Found:418.2994.
3qa:white solid,(63mg,50%),1H NMR(600MHz,CDCl3)δ:7.56(td,J=8.1,1.4Hz,1H),7.49(td,J=8.1,1.3Hz,1H),7.27-7.22(m,2H),6.94(ddd,J=16.8,10.8,4.7Hz,4H),3.62(t,J=4.5Hz,4H),2.77(t,J=4.5Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:162.6(d,J=192.1Hz),160.9(d,J=189.8Hz),133.9,133.2,132.5(t,J=9.0Hz),124.1(d,J=4.0Hz),118.2(d,J=7.6Hz),117.4(d,J=8.1Hz),117.2(dd,J=24.4,4.6Hz),67.8,67.2,50.9.11B{1H}NMR(193MHz,CDCl3)δ:14.2(1B),-4.0(1B),-11.2(8B).19F NMR(565MHz,CDCl3)δ:-111.50,-111.59.HRMS(ESI-TOF):m/z calcd for C18B10H26NOF2[M+H]+:418.2990.Found:418.2984.
3ra:white solid,(101mg,86%),1H NMR(600MHz,CDCl3)δ:3.64(t,J=4.5Hz,4H),2.72(t,J=4.5Hz,4H),2.61-2.52(m,5H),2.32(qd,J=7.4,3.8Hz,5H),1.16(dt,J=10.8,7.4Hz,7H),1.01(t,J=7.4Hz,6H).13C{1H}NMR(151MHz,CDCl3)δ:134.5,134.2,134.0,133.9,71.5,67.8,52.6,51.4,26.8,26.3 22.0,21.9,15.0,14.9,14.8,14.75.11B{1H}NMR(193MHz,CDCl3)δ:9.4(1B),-8.4(1B),-13.3(8B).HR MS(ESI-TOF):m/z calcd forC18B10H38NO[M+H]+:392.3960.Found:392.3956.
3sa:white solid,(34mg,29%),1H NMR(600MHz,CDCl3)δ:7.21(dd,J=3.7,1.1Hz,1H),7.18(d,J=5.1Hz,2H),7.15(dd,J=3.7,1.1Hz,1H),6.81(dt,J=5.0,3.8Hz,2H),3.61(t,J=3.9Hz,4H),2.76(t,J=4.2Hz,4H).13C{1H}NMR(151MHz,CDCl3)δ:135.2,134.0,133.2,132.5 129.3,127.0,126.9,75.6 67.8,66.6,51.0.11B{1H}NMR(193MHz,CDCl3)δ:13.4(1B),-5.3(1B),-11.0(8B).HRMS(ESI-TOF):m/z calcd for C14B10H24NOS2[M+H]+:394.2305.Found:394.2308.
实施例6
向15mL反应管中,依次加入化合物1t(62mg,0.3mmol)、化合物2a(93.2mg,0.45mmol)、醋酸钯(6.7mg,0.03mmol)、醋酸银(75mg,0.45mmol)和六氟异丙醇(3mL),在空气条件下将反应管密封,70℃反应36小时。待反应结束后,加入饱和碳酸氢钠溶液淬灭反应,乙酸乙酯(10mL×3)萃取,合并有机相,饱和氯化钠水溶液洗涤,无水硫酸钠干燥,抽滤,旋干,硅胶柱分离(石油醚:乙酸乙酯=7:1)得到白色固体产物3ta(23mg,26%)。1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.5Hz,4H),2.82(t,J=4.5Hz,4H),2.10(s,3H),2.01(s,3H).13C{1H}NMR(151MHz,CDCl3)δ:68.0,60.9,50.3,22.2,21.5.11B{1H}NMR(193MHz,CDCl3)δ:9.7(1B),4.9(1B),-12.2(8B).HRMS(ESI-TOF):m/z calcd for C8B10H23NOCl[M+H]+:293.2443.Found:293.2440.
实施例7
依照实施例6方法,反应条件为:1a(0.3mmol),2(0.45mmol),Pd(OAc)2(0.03mmol),AgOAc(0.45mmol),六氟异丙醇(3mL),空气氛围下70℃反应36h;通过改变反应物2,合成出各种B(9)-胺基邻碳硼烷类化合物3,具体结果如下:
3ag:white solid,(50mg,69%),1H NMR(600MHz,CDCl3)δ:2.80(q,J=6.8Hz,4H),2.07(s,3H),1.99(s,3H),0.93(t,J=7.0Hz,6H).13C{1H}NMR(151MHz,CDCl3)δ:66.9,56.8,45.4,23.8,21.2,14.1.11B{1H}NMR(193MHz,CDCl3)δ:11.3(1B),-7.4(1B),-11.3(8B).HRMS(ESI-TOF):m/z calcd for C8B10H26N[M+H]+:244.3067.Found:244.3068.
3ah:white solid,(56mg,70%),1H NMR(600MHz,CDCl3)δ:2.41(dd,J=8.7,5.2Hz,1H),2.04(s,3H),1.98(s,3H),1.88-1.80(m,2H),1.67-1.58(m,2H),1.56-1.48(m,1H),1.25-1.14(m,2H),1.07(tt,J=12.4,3.5Hz,1H),0.97-0.87(m,2H),0.69(br s,1H).13C{1H}NMR(151MHz,CDCl3)δ:67.9,57.6,55.8,36.6,25.9,25.5,23.7,21.2.11B{1H}NMR(193MHz,CDCl3)δ:10.0(1B),-6.7(1B),-11.6(8B).HRMS(ESI-TOF):m/z calcd forC10B10H28N[M+H]+:270.3225.Found:270.3217.3ai:white solid,(10mg,13%),1H NMR(600MHz,CDCl3)δ:3.59(t,J=4.8Hz,4H),2.67(t,J=4.8Hz,4H),2.29(q,J=7.6Hz,2H),2.21(q,J=7.6Hz,2H),1.18(t,J=7.6Hz,3H),1.14(t,J=7.6Hz,3H).13C{1H}NMR(151MHz,CDCl3)δ:116.4(t,J=241.6Hz),68.5,59.3,58.7,49.9(t,J=25.7Hz),23.7,21.3.11B{1H}NMR(193MHz,CDCl3)δ:10.1(1B),-6.6(1B),-11.0(8B).19F NMR(565MHz,CDCl3)δ:-123.34.HRMS(ESI-TOF):m/z calcd for C6B10H20NF2[M+H]+:252.2565.Found:252.2567.
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (4)
1.一种B(9)-胺基邻碳硼烷类化合物的合成方法,其特征在于,包括如下操作:以邻碳硼烷类化合物1和苯甲酸取代胺类化合物2为原料,在钯催化剂和银盐添加剂存在下,有机溶剂中反应,得到B(9)-胺基邻碳硼烷类化合物3;反应方程式为:
其中:R独立选自氢、C1-10烷基、苄基、氯甲基、C1-C4烷基酯、取代苯基、噻吩基、三甲基硅基,取代苯基中取代基为氢、硝基、三氟甲基、卤素、C1-C4烷基、C1-C4烷氧基中的一种或多种;或者相邻两个R基组成5-7元环烷基、苯基、四乙基苯基、苯并环烷基;R'为氢、卤素、C1-C4烷基;R1,R2分别独立选自氢、C1-C4烷基、二氟乙基、3-[4-三氟甲基苯氧基]苯丙基、甲氧乙基、C3-C7环烷基;或者R1,R2与N组成吗啉、甲基吗啉;所述钯催化剂为醋酸钯或二水合硝酸钯;银盐添加剂为醋酸银、六氟磷酸银、碳酸银或三氟甲烷磺酸银;所述有机溶剂为六氟异丙醇或三氟乙酸。
2.根据权利要求1所述B(9)-胺基邻碳硼烷类化合物的合成方法,其特征在于:所述邻碳硼烷类化合物1、苯甲酸取代胺类化合物2、钯催化剂与银盐添加剂摩尔比为1:1.2-2:0.1-0.2:1.5-2.5。
3.根据权利要求1或2所述B(9)-胺基邻碳硼烷类化合物的合成方法,其特征在于:反应无需惰性气体保护,在空气中进行。
4.根据权利要求3所述B(9)-胺基邻碳硼烷类化合物的合成方法,其特征在于:反应温度为0-80℃。
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