CN115490724A - 基于环蕃烷骨架的有机膦化合物及其用途 - Google Patents

基于环蕃烷骨架的有机膦化合物及其用途 Download PDF

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CN115490724A
CN115490724A CN202110682572.2A CN202110682572A CN115490724A CN 115490724 A CN115490724 A CN 115490724A CN 202110682572 A CN202110682572 A CN 202110682572A CN 115490724 A CN115490724 A CN 115490724A
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substituted
phenyl
reactions
reaction
aryl
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林旭锋
黄少瑛
孙伟晔
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

本发明公开了一种基于环蕃烷骨架的有机膦化合物以及基于这类化合物作为配体的金属络合物。基于环蕃烷骨架的有机膦化合物是具有通式A的化合物或所述化合物的对映体、消旋体。这些有机磷化合物可以作为配体或有机催化剂应用于有机反应或不对称反应，特别是可用于催化或不对称催化加成反应、氢化反应、偶联反应和环化反应等多种反应，具有经济实用性和工业应用前景。

Description

基于环蕃烷骨架的有机膦化合物及其用途
技术领域
本发明涉及有机合成化学技术领域，涉及基于环蕃烷骨架的有机膦化合物及其用途。该类有机磷化合物可用于金属催化的偶联反应或不对称反应，或直接催化有机反应。
背景技术
催化反应，特别是不对称催化是当今合成化学中最为活跃的研究领域之一,该技术可以最直接的、最有效的方法获得有机分子，特别是光学活性分子，具有经济性，易于实现工业化的优点。发现和发展新型高效的(手性)配体及其催化剂是实现高效高选择性的催化反应关键，也是发展新反应的创新源泉，也助力药物化学的发展。当前(手性)配体的设计合成已经取得快速发展，如下各结构式所示。因为配体的适用性有限，高度依赖反应底物，没有任何一种配体是通用的。寻求具有新型骨架配体及其催化剂是一项挑战性任务。
提高催化活性和立体选择性配体及其催化剂的设计，主要考虑电性和结构因素(如二面角、位阻和骨架刚性、柔性等)，特别是骨架和二面角对于催化的反应产率、或选择性(对映选择性、区域选择性、关环立体选择性等等)等有极大影响(EP1002801；US6333291；CN 1331871C)。产生具有不同的二面角的骨架的配体及催化剂，预示着可有不同的独特催化效果或用途。
Figure BDA0003122096450000011
Figure BDA0003122096450000021
本发明拟利用廉价易得的环蕃烷为起始原料合成的二卤环蕃烷的对映体或消旋体出发设计制备相应的环蕃烷二芳基骨架的有机膦化合物，包括双膦、双亚膦酸酚酯、双胺膦、双苄膦和双硫膦等配体及催化剂。该类骨架稳定并且刚柔并济，原料廉价丰富，合成路线短，制备成本低，实用性强，易于修饰扩大配体/催化剂库，将大大丰富膦配体及催化剂的衍生物。
发明内容
本发明的目的是提供一种基于环蕃烷骨架的有机膦化合物及其用途，并将揭示中间体和目标配体及催化的制备方法。
一种基于环蕃烷骨架的有机膦化合物，是具有如下通式A的化合物或其对映体以及消旋体：
Figure BDA0003122096450000031
其中R1-4表示4个取代基R1-R4，分别独立选自氢、卤素、硝基、氰基、酯基、C1-C10的烷基或全氟烷基、C3-C10的环烷基、C1-C6的烷氧基或全氟烷氧基、芳氧基或取代的芳氧基、杂芳氧基或取代的杂芳氧基、芳基亚甲基氧基或取代的芳基亚甲基氧基、杂芳基亚甲基氧基或取代的杂芳基亚甲基氧基、硅烷基、取代的硅烷基、芳基或取代的芳基、稠芳基或取代的稠芳基、杂芳基或取代的杂芳基以及上述的任意可能的组合取代基；其中所述取代的芳氧基、取代的芳基、取代的硅烷基、取代的稠芳基或取代的杂芳基是具有一个或多个取代基，所述取代基是独立选自卤素、N-二甲基胺基、C1-C4的烷基或全氟烷基、C3-C6的环烷基、C1-C4的烷氧基或全氟烷氧基、亚甲二氧基、芳基、芳氧基、杂芳基；所述的杂芳基是C5-C14的杂芳基；取代基R1-R4中任意相邻二个可以和苯环连接成环状体系；
其中X选自O、CH2、NR、S以及碳和磷之间的键；R选自氢、C1-C6的烷基、C3-C10的环烷基或取代的环烷基、芳基或取代的芳基、C1-C10的烷基或芳基或全氟烷基取代的磺酰基；
其中R5表示C1-C10的烷基或全氟烷基及取代的烷基或取代的全氟烷基C3-C10的环烷基及取代的环烷基、芳基亚甲基或取代的芳基亚甲基、芳基或取代的芳基、稠芳基或取代的稠芳基、杂芳基或取代的杂芳基、C1-C10的烷氧基或全氟烷氧基、C1-C10的环烷氧基或取代的环烷氧基、芳氧基或取代的芳氧基、稠芳氧基或取代的稠芳氧基、杂芳氧基或取代的杂芳氧基、芳基亚甲基氧基或取代的芳基亚甲基氧基、杂芳基亚甲基氧基或取代的杂芳基亚甲基氧基、取代的丙氧基，其中所述取代的芳氧基、取代的丙氧基、取代的芳基、取代的稠芳氧基或取代的杂芳基是具有一个或多个取代基，所述取代基是独立选自卤素、 N-二甲基胺基、C1-C4的烷基或全氟烷基、C3-C6的环烷基、C1-C4的烷氧基或全氟烷氧基、亚甲二氧基、芳基、芳氧基、杂芳基；2个R5可以组成C3-C20环状体系或取代的苯并脂肪环状体系、OR6O环状体系， R6表示联芳基、联萘基、取代的联芳基或取代的联萘基，其中取代基可以选自卤素、硝基、氰基、酯基、C1-C10的烷基或全氟烷基、C3-C10的环烷基、C1-C6的烷氧基或全氟烷氧基、芳基。
其中，通式A的对映体化合物具有的旋光纯度也可以是85％ee以上。
上述技术方案中，进一步地，X选自碳和磷之间的键，R1-4均选自氢，R5选自苯基、五氟苯基、环己基、4-甲基苯基、4-甲氧基苯基、 3,5-二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、 3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基或3,5-二(三氟甲基)-苯基；其制备方法可以是以4,12-二溴[2.2]对环芳烷的对映体或消旋体为起始原料，与各种类型的有机硼试剂经偶联反应获得环蕃烷骨架的二酚中间体、三氟甲磺酸酯化反应、与磷试剂偶联并还原获得基于环蕃烷骨架的有机膦化合物(X为无，碳和磷直接相连)，即环蕃烷二芳基骨架衍生的双膦；典型的合成路线可以如下所示；其中环蕃烷骨架的二酚中间体也可以按照文献Org. Lett.,2019,21,3682，或按照中国专利201810727287.6公开的方法进行制备。环蕃烷骨架的二酚中间体也可以按照已知经典的偶联方法，比如在镍催化下跟二芳基膦化氢偶联直接制备目标产物，相关制备方法可以类似于联萘二酚出发制备各种膦配体的过程。需要指出的是符合通式A的环蕃烷二芳基骨架衍生的双膦类有机膦化合物(X选自碳和磷之间的键)均可以按照上述方法进行制备。
Figure BDA0003122096450000051
进一步地，所述的X选自氧，R1-4均选自氢，R5选自苯基、苯氧基、环己基、4-甲基苯基、4-三氟甲基苯基、4-甲氧基苯基、3,5- 二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、 3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。制备方法是前述的环蕃烷骨架的二酚中间体在碱作用下跟二芳基氯化磷反应，即可得到基于环蕃烷骨架的有机膦化合物(X选自氧)，即环蕃烷二芳基骨架衍生的双亚膦酸酚酯。典型的反应路线可以如下所示：
Figure BDA0003122096450000052
需要指出的是，基于环蕃烷骨架的有机膦化合物(X选自硫)，也可以参照上述方法进行制备。
进一步地，X选自CH2，R1-4均选自氢，R5选自苯基、4-甲基苯基、环己基、4-三氟甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5- 二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、 3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。制备方法是二溴代环蕃烷跟有机硼试剂偶联反应，再溴代反应，再在碱作用下跟二芳基膦化氢反应，即可得到基于环蕃烷骨架的有机膦化合物(X选自CH2)，即环蕃烷二芳基骨架衍生的双苄基膦。典型的反应路线可以如下所示：
Figure BDA0003122096450000061
进一步地，X选自NH，R1-4均选自氢，R5选自苯基、4-甲基苯基、环己基、4-三氟甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5- 二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、 3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。制备方法是前述的二溴代环蕃烷跟有机硼试剂偶联反应，再在碱作用下跟二芳基膦化氢反应，即可得到基于环蕃烷骨架的有机膦化合物(X选自NH)，即环蕃烷二芳基骨架衍生的双胺膦。典型的反应路线可以如下所示：
Figure BDA0003122096450000062
本发明还提供一种包含金属和所述的基于环蕃烷骨架的有机膦化合物的金属络合物，所述金属是金、银、铜、铑、钌、铱、镍、钼、铁、铂、钯或钴。所述金属络合物的制备方法均可以参照联萘酚BINOL 衍生的各种相应膦配体金属络合物的经典合成方法。所述的金属络合物可应用于催化氢化反应或如下的反应：赫克反应、铃木-宫浦反应、熊田反应、村桥反应、胺化反应、N-芳基胺化反应，或根岸反应。
一种符合式[RuX2(二胺)A]或[Ru(中性配体)A]X的金属络合物；其中X是卤素、ClO4、SbF6、PF6、CF3SO3、BF4或CH3CO2，二胺是光学活性的1,2-二芳基乙二胺、1,2-环己二胺或1,1-二(4-甲氧基苯) -2-异丙基-1,2-乙二胺，中性配体是对伞花烃或1,5-环辛二烯，式A化合物是上述的基于环蕃烷骨架的有机膦化合物。该类金属络合物的制备方法均可以参照联萘酚衍生的膦配体金属络合物的经典合成方法。所述的金属络合物可应用于催化不对称氢化反应，且所述的底物优选自亚胺、酮、烯属不饱和化合物、烯胺、烯酰胺和乙烯基酯。
所述的基于环蕃烷骨架的有机膦化合物，作为配体或手性配体可应用于金属催化的加成反应、氢化反应、氢甲酰化反应、硼氢化反应、氢化乙烯化反应、烯烃易位反应、氢化羧基化反应、异构化反应、环丙烷化反应、迈克尔加成反应、环氧化反应、动力学拆分、狄尔斯- 阿尔德反应、硅氢化反应、不对称烯丙基化反应、环化反应、偶联反应及其不对称反应；或者所述的基于环蕃烷骨架的有机磷化合物作为有机催化剂催化环化反应。
本发明的有益效果在于：
本发明开发了一类新型的基于环蕃烷骨架的有机膦化合物，作为配体或手性配体应用于金属催化的有机反应或直接催化有机反应，特别是可作为手性的膦配体或催化剂广泛用于各类不对称催化反应中，具有经济实用性和工业应用前景。
具体实施方式
以下实施例将有助于理解本发明，但不限于本发明的内容。
通用反应条件说明：当使用了对空气敏感的试剂的所有反应均控制在充满氮气的手套箱中进行或使用标准的Schlenk技术进行。反应溶剂用通用的标准过程干燥处理。溶剂一般都在氮气氛围下进行干燥处理。相关各种基于环蕃烷骨架的有机膦化合物制备方法，均可以相应地参考基于联萘二酚衍生的各种膦配体的经典的合成过程，这对于有机合成技术人员来说，相关的合成方法均是可以类推的和参考的。
实施例1基于环蕃烷骨架的二酚合成
Figure BDA0003122096450000071
在烧瓶中加入(R)-[2.2]对环芳烷二溴(3mmol，1.10g)、间羟基苯硼酸 (15mmol，1.83g)、碳酸钠(24mmol，2.54g)、四(三苯基膦)钯(0.3mmol。 364.7mg)，氮气置换，加入二甲基亚砜(30mL)和水(3mL)，90℃下反应30小时。反应结束后，用适量1M盐酸淬灭反应，水相中的产物用乙酸乙酯萃取三次，有机相合并，用饱和NaCl溶液洗涤，然后用无水NaSO4干燥，浓缩，接着干法上样用200目硅胶柱层析(洗脱剂：乙酸乙酯：石油醚＝1：20)，即可得到白色固态的基于环蕃烷骨架的二酚(R)-B1，产率82％。1H NMR(400MHz，CDCl3)：δ＝7.23-6.23(m，14H)，4.84(s，2H)，3.53-3.46(m,2H)，3.04-2.69(m,4H)， 2.77-2.70(m,2H)。分别以(S)-[2.2]对环芳烷二溴和(±)-[2.2]对环芳烷二溴为原料，按照上述过程，制备得到了相应的(S)-B1(产率82％)和(±)-B1(产率80％)。
Figure BDA0003122096450000081
上述制备过程中，用邻羟基苯硼酸代替间羟基苯硼酸，则获得了(R)-B2，产率78％，1H NMR(400MHz,CDCl3)δ7.63(dd,J＝7.6,1.4Hz,2H),7.33–7.25(m, 2H),7.03(m,,2H),6.95(d,J＝8.1Hz,2H),6.83(d,J＝7.4Hz,2H),6.72(m,4H), 5.21(s,2H),3.22(m,2H),3.17–3.07(m,2H),2.90(m,2H),2.65(m,2H).13C NMR (101MHz,CDCl3)δ152.64,141.20,138.11,136.14,133.41,132.96,131.36,129.27, 128.40,126.95,120.45,115.49,34.53,34.32。同理用类似的方法，也制备获得了相应的(S)-B2和(±)-B2。
实施例2基于环蕃烷骨架的双三氟甲磺酸酯合成
Figure BDA0003122096450000082
在烧瓶中加入(R)-B1(2.9mmol)，氮气置换，冰水浴下加入三氟甲磺酸酐(1.1mL)、吡啶(0.6mL)和超干二氯甲烷(30mL)，升至室温反应3小时。反应结束后，用适量1M盐酸淬灭反应，静置分液，水相中有机相用二氯甲烷萃取三次，收集有机相合并，然后用无水硫酸钠干燥，浓缩，接着用100目硅胶柱层析(洗脱剂：乙酸乙酯：石油醚＝1：10)，即可得到黄色液态的产物基于环蕃烷骨架的双三氟甲磺酸酯(R)-C1，产率99％。1H NMR(400MHz,CDCl3)δ7.57 (1H),7.51–7.42(m,2H),7.30-7.34(3H),7.23(2H),6.76(d,J＝7.7Hz,2H),6.70 (dd,J＝7.7,1.5Hz,2H),6.60(d,J＝1.6Hz,2H),3.62–3.36(m,2H),3.22–3.08 (m,2H),3.00(m,2H),2.75(m,2H).13C NMR(101MHz,CDCl3)δ149.64,143.47, 139.90,138.28,137.12,135.99,133.23,130.30,129.84,129.01,121.73,119.41, 34.44,34.00.按照上述过程，改用(S)-B1和(±)-B1，则制备得到了定量的相应的 (S)-C1和(±)-C1。
Figure BDA0003122096450000091
根据类似的制备过程，则制备获得了基于环蕃烷骨架的双三氟甲磺酸酯 (R)-C2，产率98％，1H NMR(400MHz，CDCl3)：δ＝7.65-6.54(m，14H),3.12-2.85 (m，6H)，2.60-2.52(m，2H)；13C NMR(101MHz,CDCl3)δ＝147.23,139.15， 138.55，135.38，134.92，134.08，131.39，130.56，130.13，128.97，128.19，122.20， 77.34，77.03，76.71，34.50，33.93ppm。同理，制备得到了几乎定量相应的(S)-C2 和(±)-C2。
实施例3基于环蕃烷骨架的双膦合成
Figure BDA0003122096450000092
在烧瓶中加入基于环蕃烷骨架的双三氟甲磺酸酯(R)-C1(2.87mmol)、 HOPPh2(11mmol)、醋酸钯(0.28mmol)、1,4-双(二苯基膦丁烷)DPPB(0.28mmol)，氮气置换，加入二异丙基乙胺(2.4mL)、超干二甲基亚砜(30mL)，120℃反应22小时。反应结束后，用适量1M盐酸淬灭反应，静置分液，水相中产物用乙酸乙酯萃取三次，收集有机相合并，然后用无水NaSO4干燥，浓缩干，接着用 100目硅胶柱层析(洗脱剂：乙酸乙酯)，即可得到(R)-D1-1，产率87％。在单口圆底烧瓶中加入(R)-D1-1(0.42mmol)，氮气置换，加入三乙胺(0.5mL)、三氯硅烷(0.5mL)、甲苯(10mL)，100℃反应16小时。反应停止后，用适量NaOH溶液淬灭反应，静置分液，水相中产物用乙酸乙酯萃取三次，收集有机相合并，饱和食盐水洗2次，无水硫酸钠干燥，浓缩，接着用200目硅胶柱层析(洗脱剂：乙酸乙酯：石油醚＝1：50)，即可得到(R)-E1-1，产率90％。使用类似的方法，制备得到了(S)-E1-1和(±)-E1-1以及(R)-E2-1、(S)-E2-1、(±)-E2-1。
通过上述类似过程，制备得到了一系列有机膦化合物，各化合物结构和分析表征结果如下：
Figure BDA0003122096450000101
(R)-D2-1
1H NMR(400MHz,CDCl3)δ7.67-7.65(m,2H),7.54(t,J＝6.4Hz,2H),7.41–7.31(m,12H),7.29 (m,3H),7.26–7.20(m,5H),7.20–7.12(m,4H),6.37(s,2H),6.26(d,J＝7.6Hz,2H),6.12(d,J＝ 7.7Hz,2H),2.90–2.65(m,4H),2.55–2.38(m,4H).31P NMR(162MHz,CDCl3)δ26.78(s).
Figure BDA0003122096450000102
(R)-D1-1
1H NMR(400MHz,CDCl3)δ7.77–7.63(m,11H),7.61–7.48(m,5H),7.48–7.37(m,9H),7.24(d, J＝7.6Hz,2H),6.98(s,1H),6.64(d,J＝7.7Hz,2H),6.57(dd,J＝7.7,1.4Hz,2H),6.34(s,2H),3.30 –3.10(m,2H),3.02–2.91(m,2H),2.88–2.71(m,2H),2.42–2.33(m,2H).31P NMR(162MHz, CDCl3)δ29.74(s).
Figure BDA0003122096450000103
(R)-E2-1
1H NMR(400MHz,CDCl3)δ7.82–7.69(m,2H),7.46–7.38(m,2H),7.33–7.22(m,8H),7.21– 7.06(m,10H),7.02–6.87(m,6H),6.56–6.48(m,4H),6.45(s,2H),3.01–2.81(m,2H),2.79–2.64 (m,2H),2.59–2.35(m,4H).31P NMR(162MHz,CDCl3)δ-13.24(s).
Figure BDA0003122096450000104
(R)-E2-2
1H NMR(400MHz,CDCl3)δ7.75(dd,J＝6.8,4.2Hz,2H),7.39(td,J＝7.5,1.3Hz,2H),7.26(s, 1H),7.23(dd,J＝7.5,0.9Hz,1H),7.09–7.01(m,8H),7.00–6.95(m,2H),6.93(d,J＝7.5Hz,4H), 6.82(t,J＝7.6Hz,4H),6.56–6.49(m,4H),6.46(d,J＝1.2Hz,2H),2.98–2.86(m,2H),2.76–2.65 (m,2H),2.50–2.39(m,4H),2.33(s,6H),2.23(s,6H).31P NMR(162MHz,CDCl3)δ-15.33(s).
Figure BDA0003122096450000111
(R)-E2-3
1H NMR(400MHz,CDCl3)δ7.71(dd,J＝7.0,4.2Hz,2H),7.39(t,J＝7.1Hz,2H),7.30–7.21(m, 2H),6.99(dd,J＝7.2,3.1Hz,2H),6.90(s,2H),6.76(d,J＝8.8Hz,6H),6.58(d,J＝7.7Hz,4H),6.53 (d,J＝7.5Hz,2H),6.47(d,J＝9.9Hz,4H),2.92(m,2H),2.78–2.63(m,2H),2.58–2.38(m,4H), 2.22(s,12H),2.12(s,12H).31P NMR(162MHz,CDCl3)δ-12.80(t).
Figure BDA0003122096450000112
(R)-E2-4
1H NMR(400MHz,CDCl3)δ7.78–7.68(m,2H),7.38(t,J＝7.3Hz,2H),7.25–7.19(m,2H),7.07 (t,J＝7.6Hz,4H),6.97–6.90(m,2H),6.86(t,J＝7.5Hz,4H),6.80(d,J＝8.1Hz,4H),6.66(d,J＝ 8.1Hz,4H),6.51(q,J＝7.7Hz,4H),6.43(s,2H),3.79(s,6H),3.70(s,6H),2.98–2.84(m,2H),2.79 –2.64(m,2H),2.53–2.38(m,4H).31P NMR(162MHz,CDCl3)δ-16.23(s).
Figure BDA0003122096450000113
(R)-E1-1
1H NMR(400MHz,CDCl3)δ7.49–7.21(m,26H),6.98(d,J＝6.8Hz,2H),6.58(d,J＝7.7Hz,2H), 6.52(dd,J＝7.7,1.2Hz,2H),6.29(d,J＝1.3Hz,2H),3.28–3.15(m,2H),3.01–2.85(m,2H),2.81 –2.68(m,2H),2.38–2.21(m,2H).31P NMR(162MHz,CDCl3)δ-5.12(s).
Figure BDA0003122096450000114
(R)-E1-2
1H NMR(400MHz,CDCl3)δ7.33(d,J＝7.5Hz,2H),7.30–7.19(m,12H),7.11-7.16(m,8H),6.95 (d,J＝6.9Hz,2H),6.59(d,J＝7.7Hz,2H),6.52(d,J＝7.6Hz,2H),6.31(s,2H),3.31–3.15(m,2H), 3.00–2.87(m,2H),2.83–2.70(m,2H),2.30(m,14H).31P NMR(162MHz,CDCl3)δ-6.80(t).
Figure BDA0003122096450000121
(R)-E1-3
1H NMR(400MHz,CDCl3)δ7.30(dd,J＝9.3,7.5Hz,4H),7.20(dd,J＝7.6,1.6Hz,2H),6.98-7.10 (m,10H),6.91–6.82(m,4H),6.59(d,J＝7.7Hz,2H),6.52(dd,J＝7.7,1.5Hz,2H),6.15(d,J＝1.6 Hz,2H),3.33–3.18(m,2H),3.02–2.88(m,2H),2.82–2.70(m,2H),2.42–2.33(m,2H),2.21(s, 12H),2.15(s,12H).31P NMR(162MHz,CDCl3)δ-4.82(dt,J＝15.6,7.8Hz).
Figure BDA0003122096450000122
(R)-E1-4
1H NMR(400MHz,CDCl3)δ7.35–7.19(m,14H),6.96(d,J＝6.9Hz,2H),6.85-6.90(m,8H),6.59 (d,J＝7.7Hz,2H),6.53(d,J＝7.4Hz,2H),6.32(s,2H),3.76(s,6H),3.73(s,6H),3.30–3.17(m, 2H),3.00–2.87(m,2H),2.84–2.71(m,2H),2.41–2.27(m,2H).31P NMR(162MHz,CDCl3)δ -8.28(t).
实施例4基于环蕃烷骨架的双亚膦酸酚酯
Figure BDA0003122096450000123
在烧瓶中加入(R)-B1(2mmol)，氮气置换，注入超干四氢呋喃，(30mL)，冰水浴下缓缓注入正丁基锂的正己烷溶液(4毫摩尔丁基锂)、搅拌30分钟，注入二苯基氯化膦(4mmol)。反应12小时后，用1mol/L的盐酸淬灭反应，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，接着氮气氛围硅胶柱层析，得到基于环蕃烷骨架的双亚膦酸酚酯(R)-F1，产率65％，高分辨质谱确认。使用类似的方法，制备得到了相应的(S)-F1(产率62％)和(±)-F1(产率63％)。
实施例5基于环蕃烷二芳基骨架衍生的双苄基膦
Figure BDA0003122096450000131
在烧瓶中加入(R)-[2.2]对环芳烷二溴(3mmol，1.10g)，氮气置换，再加入间羟甲基苯硼酸(9mmol)、碳酸钠(10mmol，2mol/L的水溶液)、四(三苯基膦)钯(0.3mmol，364.7mg)，加入甲苯(15mL)和乙醇(15mL)，80℃下反应 5小时。反应结束后冷却到室温，用1mol/L的盐酸淬灭反应，用乙酸乙酯萃取，然后用无水NaSO4干燥，浓缩，接着氮气氛围硅胶柱层析，即可得到基于环蕃烷骨架的双苄基溴(R)-BC，产率75％，高分辨质谱确认。氮气氛围保持，在烧瓶中加入二苯基膦化氢(4mmol)，注入超干四氢呋喃(30mL)，冰水浴下缓缓注入正丁基锂的正己烷溶液(4毫摩尔丁基锂)、搅拌30分钟，加入(R)-BC(2mmol)。反应12小时后，用1mol/L的盐酸淬灭反应，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，接着氮气氛围硅胶柱层析(洗脱剂：乙酸乙酯/石油醚)，得到基于环蕃烷骨架的双苄基膦(R)-G1，产率75％，高分辨质谱确认。使用类似的方法，制备得到了相应的(S)-G1(总产率42％)和(±)-G1(总产率45％)。
实施例6基于环蕃烷二芳基骨架衍生的双胺膦
Figure BDA0003122096450000132
在烧瓶中加入(R)-[2.2]对环芳烷二溴(3mmol，1.10g)，氮气置换，再加入间胺基苯硼酸单水合物(9mmol)、碳酸钠(10mmol，2mol/L的水溶液)、四(三苯基膦)钯(0.3mmol，364.7mg)，加入1,2-二甲氧基乙烷(15mL)，80℃下反应24小时。反应结束后冷却到室温，用1mol/L的盐酸淬灭反应，用乙酸乙酯萃取，然后用无水NaSO4干燥，浓缩，接着氮气氛围硅胶柱层析，即可得到基于环蕃烷骨架的双胺(R)-BD，产率78％，高分辨质谱确认。氮气氛围保持，在烧瓶中加入二苯基氯化膦(4mmol)，注入超干四氢呋喃(30mL)，加入(R)-BD (1mmol)，冰水浴下缓缓注入三乙胺(8毫摩尔)，搅拌30分钟，再室温反应 12小时后，用1mol/L的盐酸淬灭反应，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，接着氮气氛围硅胶柱层析(洗脱剂：乙酸乙酯/石油醚)，得到基于环蕃烷骨架的双胺(R)-H1，产率55％，高分辨质谱确认。使用类似的方法，制备得到了相应的(S)-H1(总产率40％)和(±)-H1(总产率45％)。
实施例7
一种包含金属和通式A化合物或其对映体以及消旋体的金属络合物的通用合成过程，PdCl2[(R)-E1-1]的合成：在氮气氛围下，向反应瓶中加入双膦配体 (R)-E1-1(0.178mmol)和2毫升苯，搅拌溶解充分，然后加入含有46毫克的二乙腈合氯化钯(0.178mmol,PdCl2(MeCN)2)的4毫升苯溶液。回流搅拌2小时，旋蒸除去溶剂，真空干燥得到PdCl2[(R)-E1-1]络合物，收率100％。使用类似的方法，制备得到了定量收率相应的PdCl2[(±)-E1-1]络合物，PdCl2[(R)-E2-1]络合物，PdCl2[(±)-E2-1]络合物。
实施例8
一种符合式[RuX2(二胺)A]络合物的通用合成过程：在氮气氛围的手套箱中称取双膦配体(R)-E1-1(0.160mmol)和[Ru(C6H6)Cl2]2(0.08mmol,40mg)，加入到Schlenk反应管中。然后在氮气氛围下注入3毫升的干燥脱气的N,N-二甲基甲酰胺，搅拌下加热到100度反应2小时，接着冷却到室温后，加入(R,R)-1,2- 二苯基乙二胺((R,R)-DPEN,0.160mmol)，该反应继续室温搅拌12小时。使用减压真空脱去溶剂并干燥，即得定量的固体产物RuCl2-[(R)-E1-1][(R,R)-DPEN], 使用类似的方法，制备得到了定量收率相应的RuCl2-[(S)-E1-1][(R,R)-DPEN]、 RuCl2-[(R)-E2-1][(R,R)-DPEN]和RuCl2-[(S)-E2-1][(R,R)-DPEN]。测试不对称氢化的实验过程：以10毫升异丙醇为溶剂，依次加入1mmol苯乙酮，加入1mmol 叔丁醇钾和RuCl2-[(R)-E1-1][(R,R)-DPEN]，在35度于30个大气压下进行氢化反应12小时，彻底转化为还原产物2-甲基苯甲醇，取样进行手性GC测试产物的ee值高达95％以上。
实施例9
Figure BDA0003122096450000141
氮气保护下，在反应管中，加入醋酸钯(5％eq,0.005mmol)，双膦配体(±)-E1-1(5％eq,0.005mmol)，甲苯1mL，室温反应1h进行原位制备络合物。接着，依次加入N-乙酰基邻叔丁基苯胺底物S1(1eq,0.1mmol)，苯基烯丙基醋酸酯 S2(2eq,0.2mmol)，叔丁醇钾(0.24mmol)，室温下反应24小时，反应完全。反应混合物直接柱层析(乙酸乙酯和石油醚作为混合洗脱剂)，获得N-乙酰基 -N-苯基烯丙基邻叔丁基苯胺P1，产率90％，1H NMR(400MHz,CDCl3)δ7.58(dd, J＝8.1,1.4Hz,1H),7.38–7.33(m,2H),7.31(dd,J＝10.1,4.6Hz,3H),7.26–7.21 (m,1H),7.17–7.12(m,1H),6.92(dd,J＝7.8,1.5Hz,1H),6.48–6.29(m,2H),5.12 (dd,J＝14.2,4.5Hz,1H),3.46(dd,J＝14.0,7.9Hz,1H),1.81(s,3H),1.41(s,9H). 采用类似的反应过程，仅把(±)-E1-1用(±)-E2-1代替，则P1产率为88％。
实施例10
Figure BDA0003122096450000151
氮气保护下，在反应管中，加入醋酸钯(5％eq,0.005mmol)，膦配体(R)-E1-1 (5％eq,0.005mmol)，甲苯1mL，室温反应1h进行原位制备络合物。接着，依次加入N-Ts-邻叔丁基苯胺底物S3(1eq,0.1mmol)，苯基烯丙基醋酸酯S2(2eq, 0.2mmol)，叔丁醇钾(0.24mmol)，室温下反应24小时，反应完全。反应混合物直接柱层析(乙酸乙酯和石油醚作为混合洗脱剂)，获得N-Ts-N-苯基烯丙基邻叔丁基苯胺P2，产率98％，并且30％ee；1H NMR(400MHz,CDCl3)δ7.65(d, J＝8.2Hz,2H),7.57(dd,J＝8.2,1.4Hz,1H),7.31–7.26(m,4H),7.25–7.15(m, 4H),7.05–6.93(m,1H),6.49(dd,J＝7.9,1.3Hz,1H),6.33(d,J＝15.8Hz,1H),6.17–6.02(m,1H),4.36–4.26(m,1H),4.25–4.16(m,1H),2.44(s,3H),1.55(s, 9H)。采用类似的反应过程，仅把(R)-E1-1用(R)-E2-1代替，则P2产率为95％， 70％ee。
实施例11
Figure BDA0003122096450000152
氮气保护下，在反应管中，加入PdCl2(10％,0.01mmol)，膦配体L(10％,0.01mmol)，乙醇1mL，室温搅拌1h进行络合，然后加入炔基苯胺底物S4(1eq, 0.1mmol)，80℃下反应4h。旋干溶剂，直接硅胶柱层析纯化产物，获得轴手性产物P3，85％yield,60％ee；手性色谱条件是chrialpak IA column,i-PrOH/Hexane＝ 0.5/99.5,flow rate＝0.5mL,254nm.t1(major)＝13.2min；t2(minor)＝15.2min。
实施例12
Figure BDA0003122096450000161
氮气保护，在Schlenk管中加入双膦配体(R)-E2-1(0.01mmol)、[Pd(C3H5)Cl]2(0.005mmol)，加入二氯甲烷溶液(1mL)，室温搅拌2h，然后加入1,3-二苯基-2-烯丙基醋酸酯S5(0.1mmol)；接着用针管添加预先准备好的混合0.5h的甲苯(1mL)、丙二酸二乙酯(0.3mmol)和ZnEt2(300uL,1M in hexane)混合液，然后在室温反应4小时，用饱和NH4Cl溶液淬灭，静置分液，水相用乙酸乙酯萃取3次，收集有机相合并，然后用饱和食盐水洗，无水NaSO4干燥。接着用旋蒸仪浓缩，然后用200目硅胶柱层析纯化(洗脱剂：乙酸乙酯：石油醚＝1： 10)，得到反应产物P4，96％yield,70％ee；chrialpak IA column,i-PrOH/Hexane＝15/85,flow rate＝1mL,254nm.t1(minor)＝6.8min；t2(major)＝8.4min.。按照类似的反应过程，分别依次用(R)-F1、(R)-G1和(R)-H1代替(R)-E2-1，则所得目标产物的产率依次为85％、 95％和90％，而ee值分别依次是55％、65％和75％。
实施例13
Figure BDA0003122096450000162
氮气氛围下，在反应瓶中加入膦配体(±)-E1-1(0.25mmol)，加入5毫升乙醇，回流搅拌溶解，把该溶液缓缓加入到溶解了HAuCl4·4H2O(206mg,0.5mmol) 的3毫升乙醇溶液，接着室温反应搅拌2小时后，抽滤，滤饼溶解在5毫升二氯甲烷中，然后加入50毫升石油醚析出沉淀物，抽滤，滤饼真空干燥得到一价金盐的络合物[(±)-E1-1][AuCl]2，收率61％。然后，氮气氛围下，在反应瓶中依次加入0.2mmol的二酮底物S6和0.3mmol的苯乙烯、0.015mmol[(±)-E1-1][AuCl]2，和0.03mmol的三氟甲磺酸银以及2毫升溶剂硝基甲烷，回流反应16小时，产物直接用柱层析纯化得到目标产物P5，产率92％。
实施例14
Figure BDA0003122096450000163
氮气氛围下，在反应瓶中加入(±)-E2-1(0.025mmol)和0.5毫摩尔的丙二烯基甲酸乙酯(In-2)以及0.5毫摩尔的烯烃In-1，注入3毫升甲苯，搅拌反应24小时，反应液直接硅胶柱层析，获得[3+2]的环化产物In-3，收率68％。
实施例15
Figure BDA0003122096450000171
在氮气氛围下，向反应瓶加入0.06mmol的三氟甲磺酸铜和0.03mmol的(±)- E2-1，注入1毫升的1,2-二氯乙烷，室温搅拌30分钟得到三氟甲磺酸铜和(±)-E2-1 的络合物(2:1组成)；接着加入0.5mmol的2-(1-苯乙烯基)苯甲酸S7和1mmol 的吗啉苯甲酸酯S8，回流反应3小时，然后冷却后直接用硅胶柱层析(乙酸乙酯:石油醚＝1:2)纯化得到环化反应的目标产物P6，收率90％。
实施例16
Figure BDA0003122096450000172
0.03毫摩尔的[Rh(COD)2BF4]和0.03毫摩尔的(±)-E2-1在10毫升二氯甲烷中搅拌反应30分钟获得络合物，然后注入含有5毫摩尔A-1的10毫升二氯甲烷，保持5个标准大气压的氢气压力下进行室温还原反应，24小时结束反应，纯化后可以得到100％的产物A-2。
实施例17
Figure BDA0003122096450000173
一般过程：在手套箱中通过在19.2毫升二氯甲烷中混合0.008毫摩尔(3.7毫克)的[Rh(COD)2PF6]和膦配体(0.8毫升膦配体的10mg/ml的甲苯溶液，0.012毫摩尔)原位制备铑-膦络合物，该混合物搅拌反应30分钟获得络合物，然后将2.5 毫升该溶液转移到含有0.1毫摩尔烯酰胺底物A-3反应管中。在室温下于25psi 氢气压力下进行氢化反应24小时，反应全部完成，生成定量的产物A-4。用手性GC测试对映体过量，结果如下：使用膦配体(R)-F1，达到81％ee；使用膦配体(R)-G1，达到75％ee；使用膦配体(R)-H1，达到91％ee；使用(±)-F1，产率100％。
实施例18
氢甲酰化反应测试过程：使用1-己烯为底物，进行本体反应，Rh(acac)(CO)2浓度为1mM，膦配体(±)-G1浓度为0.41M，90psig(6.2bar,1:1 H2/CO),反应温度 90度，12小时持续反应，获得相应的氢甲酰化产物，产率91％。

Claims (10)

1.一种基于环蕃烷骨架的有机膦化合物，其特征在于，是具有如下通式A的化合物或其对映体以及消旋体：
Figure FDA0003122096440000011
其中R1-4表示4个取代基R1-R4，分别独立选自氢、卤素、硝基、氰基、酯基、C1-C10的烷基或全氟烷基、C3-C10的环烷基、C1-C6的烷氧基或全氟烷氧基、芳氧基或取代的芳氧基、杂芳氧基或取代的杂芳氧基、芳基亚甲基氧基或取代的芳基亚甲基氧基、杂芳基亚甲基氧基或取代的杂芳基亚甲基氧基、硅烷基、取代的硅烷基、芳基或取代的芳基、稠芳基或取代的稠芳基、杂芳基或取代的杂芳基以及上述的任意可能的组合取代基；其中所述取代的芳氧基、取代的芳基、取代的硅烷基、取代的稠芳基或取代的杂芳基具有一个或多个取代基，所述取代基独立选自卤素、N-二甲基胺基、C1-C4的烷基或全氟烷基、C3-C6的环烷基、C1-C4的烷氧基或全氟烷氧基、亚甲二氧基、芳基、芳氧基、杂芳基；所述的杂芳基是C5-C14的杂芳基；取代基R1-R4中任意相邻两个取代基和苯环连接成环状体系；
其中X选自O、CH2、NR、S或无；R选自氢、C1-C6的烷基、C3-C10的环烷基或取代的环烷基、芳基或取代的芳基、C1-C10的烷基或芳基或全氟烷基取代的磺酰基；
其中R5表示C1-C10的烷基或全氟烷基及取代的烷基或取代的全氟烷基C3-C10的环烷基及取代的环烷基、芳基亚甲基或取代的芳基亚甲基、芳基或取代的芳基、稠芳基或取代的稠芳基、杂芳基或取代的杂芳基、C1-C10的烷氧基或全氟烷氧基、C1-C10的环烷氧基或取代的环烷氧基、芳氧基或取代的芳氧基、稠芳氧基或取代的稠芳氧基、杂芳氧基或取代的杂芳氧基、芳基亚甲基氧基或取代的芳基亚甲基氧基、杂芳基亚甲基氧基或取代的杂芳基亚甲基氧基、取代的丙氧基，其中所述取代的芳氧基、取代的丙氧基、取代的芳基、取代的稠芳氧基或取代的杂芳基具有一个或多个取代基，所述取代基独立选自卤素、N-二甲基胺基、C1-C4的烷基或全氟烷基、C3-C6的环烷基、C1-C4的烷氧基或全氟烷氧基、亚甲二氧基、芳基、芳氧基、杂芳基；2个R5组成C3-C20环状体系或取代的苯并脂肪环状体系、OR6O环状体系，R6表示联芳基、联萘基、取代的联芳基或取代的联萘基，其中取代基可以选自卤素、硝基、氰基、酯基、C1-C10的烷基或全氟烷基、C3-C10的环烷基、C1-C6的烷氧基或全氟烷氧基、芳基。
2.如权利要求1所述的基于环蕃烷骨架的有机膦化合物或其对映体以及消旋体，其特征在于，X为无，此时碳和磷直接相连，R1-4均为氢，R5选自苯基、五氟苯基、环己基、4-甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基或3,5-二(三氟甲基)-苯基。
3.如权利要求1所述的基于环蕃烷骨架的有机膦化合物或其对映体以及消旋体，其特征在于，X为氧，R1-4均为氢，R5选自苯基、苯氧基、环己基、4-甲基苯基、4-三氟甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。
4.如权利要求1所述的基于环蕃烷骨架的有机膦化合物或其对映体以及消旋体，其特征在于，X为CH2，R1-4均为氢，R5选自苯基、4-甲基苯基、环己基、4-三氟甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。
5.如权利要求1所述的基于环蕃烷骨架的有机膦化合物或其对映体以及消旋体，其特征在于，X为NH，R1-4均为氢，R5选自苯基、4-甲基苯基、环己基、4-三氟甲基苯基、4-甲氧基苯基、3,5-二甲基苯基、3,5-二甲基-4-甲氧基-苯基、3,4,5-三甲基-苯基、3,4,5-三甲氧基-苯基、3,5-二叔丁基-4-甲氧基-苯基、3,5-二(三氟甲基)-苯基、3,5-二叔丁基-苯基或4-二甲氨基-苯基。
6.一种金属络合物，其特征在于，包含金属和如权利要求1所述的基于环蕃烷骨架的有机膦化合物，所述金属是金、银、铜、铑、钌、铱、镍、钼、铁、铂、钯或钴。
7.根据权利要求6所述的金属络合物，其特征在于，应用于催化氢化反应或如下的反应：赫克反应、铃木-宫浦反应、熊田反应、村桥反应、胺化反应、N-芳基胺化反应，或根岸反应。
8.一种符合式[RuX2(二胺)A]或[Ru(中性配体)A]X的金属络合物，其特征在于，其中X是卤素、ClO4、SbF6、PF6、CF3SO3、BF4或CH3CO2，二胺是光学活性的1,2-二芳基乙二胺、1,2-环己二胺或1,1-二(4-甲氧基苯)-2-异丙基-1,2-乙二胺，中性配体是对伞花烃或1,5-环辛二烯，式中A化合物是如权利要求2所述的基于环蕃烷骨架的有机膦化合物。
9.如权利要求8所述的一种符合式[RuX2(二胺)A]或[Ru(中性配体)A]X的金属络合物，其特征在于，应用于催化不对称氢化反应，且所述的底物选自亚胺、酮、烯属不饱和化合物、烯胺、烯酰胺和乙烯基酯。
10.如权利要求1所述的基于环蕃烷骨架的有机膦化合物，其特征在于，作为配体或手性配体应用于金属催化的加成反应、氢化反应、氢甲酰化反应、硼氢化反应、氢化乙烯化反应、烯烃易位反应、氢化羧基化反应、异构化反应、环丙烷化反应、迈克尔加成反应、环氧化反应、动力学拆分、狄尔斯-阿尔德反应、硅氢化反应、不对称烯丙基化反应、环化反应、偶联反应及其不对称反应；或者作为有机催化剂催化环化反应。
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