CN113354820B - 一种手性聚硅醚及其合成方法与应用 - Google Patents

一种手性聚硅醚及其合成方法与应用 Download PDF

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CN113354820B
CN113354820B CN202010147708.5A CN202010147708A CN113354820B CN 113354820 B CN113354820 B CN 113354820B CN 202010147708 A CN202010147708 A CN 202010147708A CN 113354820 B CN113354820 B CN 113354820B
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copper
polysiloxane
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CN113354820A (zh
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周永贵
王晓清
孙蕾
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Dalian Institute of Chemical Physics of CAS
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    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C08G77/52—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

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Abstract

本发明公开了一种手性聚硅醚及其合成方法与应用，属于含硅高分子合成技术领域。其用到的催化剂是铜氢手性双膦配合物。通过该方法可以得到高光学纯手性聚硅醚高分子(对映体过量可达99％，产率大于95％)。本发明可以实现廉价金属催化，操作简单易行，条件温和，原子利用率百分百，环境友好。

Description

一种手性聚硅醚及其合成方法与应用
技术领域
本发明涉及一种手性聚硅醚及其合成方法与应用，属于含硅高分子合成技术领域。
背景技术
主链含硅氧结构的高分子已广泛应用于制备柱分离消旋体中。(参考文献一：(a)Frank,H.；Nicholson,G.J.；Bayer,E.J.Chromatogr.Sci.1997,15,174-176.(b)Spallek,M.J.；Storch,G.；Trapp,O.Eur.J.Org.Chem.2012,3929–3945.(c)Zimmermann,A.；Horak,J.；Sievers-Engler,A.；Sanwald,C.；Lindner,W.；Kramer,M.；Lammerhofer,M.J.Chromatogr.A 2016,1436,73-83.)。其中，聚硅醚是一类重要的主链含硅氧结构的高分子，他主要合成方法是加聚反应和缩聚反应。(参考文献二：(a)Liaw,D.-J.Polymer1997,38,5217-5219.(b)Minegishi,S.；Ito,M.；Nishikubo,T.；Kameyama,A.J.Polym.Sci.,Part A:Polym.Chem.2000,38,2254-2259.(c)Sahmetlioglu,E.；Nguyen,H.T.H.；Nsengiyumva,O.；Gokturk,E.；Miller,S.A.ACS Macro Lett.2016,5,466-470.(d)Cheng,C.；Watts,A.；Hillmyer,M.A.；Hartwig,J.F.Angew.Chem.,Int.Ed.2016,55,11872-11876.)。近年来，通过原子利用率更高的硅氢化反应合成聚硅醚，引起了人们的注意，相比其他方法，它的优势在于原子利用率高、条件温和。但目前发展的方法底物范围受限。(参考文献三：(a)
Figure BDA0002401340770000011
G.；
Figure BDA0002401340770000012
-Alvarez，F.J.；Iglesias，M.；Horna，C.；Vispe，E.；Sancho，R.；Lahoz，F.J.；Iglesias，M.；Pérez-Torrente,J.J.；Oro,L.Catal.Sci.Technol.2014,4,62-70.(b)Li,C.；Hua,X.；Mou,Z.；Liu,X.；Cui,D.Macromol.Rapid Commun.2017,38,1700590.(c)Vijjamarri,S.；Chidara,V.K.；Du,G.ACS Omega 2017,2,582-591.(d)Sample,C.A.；Lee,S.-H.；Bates,M.W.；Ren,J.M.；Lawrence,J.；Lensch,V.；Gerbec,J.A.；Bates,C.M.；Li,S.；Hawker,C.J.Macromolecules2019,52,1993-1999.)。虽然消旋版本的聚硅醚的合成已经得到了一定的发展，但其手性版本的研究却很少又被报道，只有Kawakami教授于2000年报道了有光学活性的聚硅醚的合成，但合成的聚硅醚不稳定，底物范围窄，且最高仅取得40％ee。(参考文献四：(a)Li,Y.；Seino,M.；Kawakami,Y.Macromolecules 2000,33,5311-5314.)。
发明内容
本发明设想能否通过铜催化硅烷和二酮的不对称硅氢化反应实现高光学纯手性聚硅醚的合成。
本发明的目的是提供一种手性聚硅醚及其合成方法与应用。
本发明操作简便实用，原料易得，原子利用率百分之百，所得聚硅醚具有高光学纯度、产率好，热稳定性良好等优点。
为实现上述目的，本发明以铜氢双膦配体为催化剂，以原料易得的硅烷和二酮类化合物为底物，通过硅氢化反应实现高光学纯手性聚硅醚的合成。
本发明提供了一种手性聚硅醚，包括式(Ⅰ)或式(Ⅱ)所示具有硅氧键结构的重复单元：
Figure BDA0002401340770000021
其中，R1为
Figure BDA0002401340770000022
R2为
Figure BDA0002401340770000023
Figure BDA0002401340770000024
R3为-Ph或-Me；
R4为甲基、乙基、丙基、异丙基、正丁基、异丁基或芳基。
本发明还提供了一种手性聚硅醚的合成方法，所述合成方法以[Cu]为前体，以铜氢双膦配体L为催化剂，在有机溶剂中，实现硅烷单体和二酮单体的不对称硅氢化聚合，形成具有硅氧键结构的手性聚硅醚；
所述[Cu]为叔丁醇亚铜、醋酸铜、环己丁酸铜、醋酸亚铜中的至少一种；
所述铜氢双膦配体L为L1～L4中的一种：
Figure BDA0002401340770000031
所述硅烷单体为1a-1e中的一种：
Figure BDA0002401340770000032
所述二酮单体为2a-2i中的一种：
Figure BDA0002401340770000033
其中，R4为甲基、乙基、丙基、异丙基、正丁基、异丁基、芳基中的一种。
进一步地，所述有机溶剂为甲苯、甲基叔丁基醚、四氢呋喃、1,4-二氧六环、均三甲苯中的至少一种。
基于以上技术方案，优选的，所述方法的具体反应步骤为：
在氮气保护下，向封管中加入[Cu]、铜氢双膦配体L和有机溶剂，于室温搅拌反应0.5-2h后，氮气保护下加入硅烷单体和二酮单体，于30-80℃搅拌反应24-48h后，旋干溶剂，用二氯甲烷、甲醇按体积比为0.5:5-0.5:10沉淀聚合物，沉淀分离得到高光学纯手性聚硅醚产物。
基于以上技术方案，优选的，所述聚合物的光学纯度表征步骤为：
向反应瓶中加入聚合物(0.15mmol)、氢氧化钠溶液(4mL,3N)、甲醇(4mL)和四氢呋喃(4mL)，于室温搅拌反应12h后，分离目标产物二醇，通过核磁确定结构，HPLC确定光学纯度。
基于以上技术方案，优选的，所述[Cu]、铜氢双膦配体L、硅烷单体、二酮单体的摩尔比为：0.005～0.025:0.005～0.025:1:1。
基于以上技术方案，优选的，所述硅烷单体和二酮单体在溶剂中的浓度分别为0.1～1.0mmol/mL。
本发明还提供了手性聚硅醚在不对称催化、手性分离中的应用。
发明有益效果
本发明具有以下优点
1.反应活性和对映选择性高。
2.能得到高光学纯、热稳定性质好的手性聚硅醚。
3.催化剂商业可得，反应操作简便。
4.反应条件温和，适用范围广。
具体实施方式
下述非限定性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1-9
条件的优化：
改变配体、有机溶剂的种类。
在氮气保护下，向封管中加入环己丁酸铜、配体L(环己丁酸铜与配体的摩尔比为1:1)和有机溶剂，于室温搅拌反应2h后，氮气下加入摩尔比为1:1的硅烷单体1a和二酮单体2a，于30℃搅拌反应24h后，旋干溶剂，用二氯甲烷、甲醇体系(体积比为0.5/5)沉淀聚合物，沉淀分离得到纯的高光学纯手性聚硅醚产物3aa。向反应瓶中加入聚硅醚产物(0.15mmol)、氢氧化钠溶液(4mL,3N)、甲醇(4mL)和四氢呋喃(4mL,3N)，于室温搅拌反应12h后，分离目标产物二醇4aa，通过核磁确定结构，HPLC确定光学纯度，反推聚合物的光学纯度。
改变配体、有机溶剂的种类，具体结果如表1。
Figure BDA0002401340770000051
表1.高光学纯手性聚硅醚合成的优化
Figure BDA0002401340770000052
实施例10-22
合成一系列高光学纯手性聚硅醚产物。
在氮气保护下，向封管中加入环己丁酸铜(化合物1用量的0.5mol％)、配体L(化合物1用量的0.5mol％)和甲基叔丁基醚，于室温搅拌反应2h后，氮气下加入硅烷单体(化合物1)和二酮单体(化合物2)(摩尔比1:1)，于30℃搅拌反应24h后，旋干溶剂，用二氯甲烷、甲醇体系沉淀聚合物，沉淀分离得到纯的高光学纯手性聚硅醚产物。向反应瓶中加入聚硅醚产物(0.15mmol)、氢氧化钠溶液(4mL,3N)、甲醇(4mL)和四氢呋喃(4mL,3N)，于室温搅拌反应12h后，分离目标产物二醇，通过核磁确定结构，HPLC确定光学纯度，反推聚合物的光学纯度。改变反应中硅烷和二酮单体的种类得到13个不同的实施例，改变的种类具体见表2。
本实施例中手性聚硅醚产物的分析数据详见：3aa、3ba、3ca、3da、3ea、3ca-1、3ca-2、3ca-3、3ca-4、3ca-5、3ca-6、3ca-7、3cb、3cc、3cg、3cf、3ch、3cd、3ce、3ci。
本实施例中产物二醇的分析数据详见：4aa、4ba、4ca、4da、4ea、4ca-1、4ca-2、4ca-3、4ca-4、4ca-5、4ca-6、4ca-7、4cb、4cc、4cg、4cf、4ch、4cd、4ce、4ci。
所述化合物1选自：
Figure BDA0002401340770000061
所述化合物2选自：
Figure BDA0002401340770000062
其中，R4为甲基、乙基、丙基、异丙基、正丁基、异丁基、芳基中的至少一种。
所述配体L为：
Figure BDA0002401340770000071
表2.用一系列硅烷和二酮合成聚硅醚
Figure BDA0002401340770000072
Polysilyether(3aa):322mg,87％yield,colorless soft solid,new compound,[α]20 D＝+109.82(c 0.57,THF).
Figure BDA0002401340770000073
Polysilyether(3ba):374mg,84％yield,colorless soft solid,new compound,[α]20 D＝+56.74(c 0.89,THF).1H
Figure BDA0002401340770000074
Polysilyether(3ca):414mg,96％yield,foamy solid,new compound,[α]20 D＝+181.72(c 0.81,THF).1H NMR(400MHz,CDCl3)δ7.58(s,4H),7.54(d,J＝8.2Hz,4H),7.38(d,J＝8.2Hz,4H),4.98-4.83(m,2H),
Figure BDA0002401340770000081
Polysilyether(3da):421mg,99％yield,colorless soft solid,new compound,[α]20 D＝+355.42(c 0.68,THF).
Figure BDA0002401340770000082
Polysilyether(3ea):331mg,92％yield,colorless soft solid,new compound,[α]20 D＝+221.41(c 0.42,THF).
Figure BDA0002401340770000083
Polysilyether(3ca-1):386mg,84％yield,foamy solid,new compound,[α]20 D＝+146.66(c 0.60,THF).1H NMR(400MHz,CDCl3)δ7.60-7.46(m,8H),7.32(d,J＝7.9Hz,4H),4.61(t,J＝6.1Hz,2H),1.91–1.63(m,
Figure BDA0002401340770000084
Polysilyether(3ca-2):473mg,97％yield,foamy solid,new compound,[α]20 D＝+148.30(c 0.83,THF).1H NMR(400MHz,CDCl3)δ7.60-7.52(m,8H),7.43-7.31(m,4H),4.77-4.63(m,2H),1.85-1.74(m,2H),
Figure BDA0002401340770000085
Polysilyether(3ca-3):476mg,98％yield,foamy solid,new compound,[α]20 D＝+126.46(c 0.34,THF).1H NMR(400MHz,CDCl3)δ7.54-7.48(m,8H),7.28(d,J＝8.2Hz,4H),4.35(d,J＝6.4Hz,2H),1.98-1.85(m,
Figure BDA0002401340770000086
Polysilyether(3ca-4):497mg,96％yield,foamy solid,new compound,[α]20 D＝+105.47(c 0.42,THF).1H NMR(400MHz,CDCl3)δ7.63-7.48(m,8H),7.35(d,J＝8.0Hz,4H),4.70(t,J＝6.2Hz,2H),1.86-1.76(m,
Figure BDA0002401340770000087
Polysilyether(3ca-5):489 mg,95％yield,foamy solid,new compound,[α]20 D＝+86.35(c 0.43,THF).1H NMR(400MHz,CDCl3)δ7.56-7.48(m,8H),7.31(d,J＝8.1Hz,4H),4.75-4.66(m,2H),1.79-1.65(m,4H),
Figure BDA0002401340770000091
Polysilyether(3ca-6):543mg,98％yield,foamy solid,new compound,[α]20 D＝+39.50(c 0.60,THF).1H NMR(400MHz,CDCl3)δ7.55-7.45(m,8H),7.39-7.32(m,
Figure BDA0002401340770000092
Polysilyether(3ca-7):600mg,98％yield,foamy solid,new compound,[α]20 D＝+107.33(c 0.60,THF).1H
Figure BDA0002401340770000093
Polysilyether(3cb):395mg,91％yield,colorless soft solid,new compound,[α]20 D＝+108.45(c 0.39,THF).
Figure BDA0002401340770000094
Polysilyether(3cc):299mg,67％yield,colorless soft solid,new compound,[α]20 D＝+112.49(c 0.40,THF).
1H NMR(400 MHz,CDCl3)δ7.56-7.51(m,4H),7.24-7.15(m,4H),7.14-7.00(m,4H),4.83(q,J＝6.3Hz,2H),
Figure BDA0002401340770000095
Polysilyether(3cg):248mg,70％yield,colorless soft solid,new compound,[α]20 D＝+115.52(c 0.43,THF).
Figure BDA0002401340770000096
Polysilyether(3cf):235mg,66％yield,colorless soft solid,new compound,[α]20 D＝+73.24(c 0.40,THF).1H
Figure BDA0002401340770000097
Polysilyether(3ch):372mg,83％yield,colorless soft solid,new compound,[α]20 D＝+44.63(c 0.54,THF).1H
Figure BDA0002401340770000098
Polysilyether(3cd):354mg,85％yield,yellow solid,new compound,[α]20 D＝+102.10(c 0.38,THF).1H NMR(400 MHz,CDCl3)δ7.60(s,4H),6.38(d,J＝3.3Hz,2H),
Figure BDA0002401340770000101
Polysilyether(3ce):427mg,96％yield,green solid,new compound,[α]20 D＝+71.31(c 0.38,THF).1H NMR
Figure BDA0002401340770000102
Polysilyether(3ci):175mg,49％yield,colorless soft solid,new compound,[α]20 D＝+78.11(c 0.43,THF).1H
Figure BDA0002401340770000103
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(ethan-1-ol)(4aa):Thereaction was conducted by using polysilyether 3aa(44.5mg,0.12mmol),affording4aa 21.9mg,76％yield,white solid,known compound[6],99％
Figure BDA0002401340770000104
(100MHz,CDCl3)δ145.0，140.2，127.4，126.0，70.3，25.3.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝60/40,flow＝0.7mL/min,retention time 12.1min,14.3min(meso)and 17.9min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(ethan-1-ol)(4ba):Thereaction was conducted by using
Figure BDA0002401340770000105
(meso)and 17.4min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(ethan-1-ol)(4ca):Thereaction was conducted by using
Figure BDA0002401340770000106
℃,n-Hexane/i-PrOH＝60/40,flow＝0.7mL/min,retention time 12.0min,14.3(meso)min and17.9min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(ethan-1-ol)(4da):Thereaction was conducted by using
Figure BDA0002401340770000107
℃,n-Hexane/i-PrOH＝60/40,flow＝0.7mL/min,retention time 11.9min,14.1min(meso)and17.4min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(ethan-1-ol)(4ea):Thereaction was conducted by using
Figure BDA0002401340770000108
(meso)and 17.5min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(propan-1-ol)(4ca-1):Thereaction was conducted by using polysilyether 3ca-1(69.0mg,0.15mmol),affording 4ca-1 39.2mg,97％yield,white solid,known compound[7],
Figure BDA0002401340770000111
CDCl3)δ143.8,140.2,127.2,126.6,75.9,32.0,10.3.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.7mL/min,retention time 12.0min,16.1min(meso)and 24.6min(major).
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(butan-1-ol)(4ca-2):Thereaction was conducted by using polysilyether 3ca-2(50.3mg,0.10mmol),affording 4ca-2 23.8mg,80％yield,white solid,mp＝106-107℃,
Figure BDA0002401340770000112
(s,2H),1.91-1.79(m,2H),1.75-1.68(m,2H),1.54-1.42(m,2H),1.41-1.30(m,2H),0.95(t,J＝7.4Hz,6H).13C NMR(100MHz,CDCl3)δ144.1，140.2，127.2，126.5，74.3，41.3，19.2，14.1.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.7mL/min,retention time 10.9 min,13.3 min(meso)and 20.3 min(major).HRMS:Calculated for C20H26O2Na[M+Na]+321.1825,found:321.1828.
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(2-methylpropan-ol)(4ca-3):The reaction was conducted by using polysilyether 3ca-3(73.2mg,0.15mmol),affording 4ca-3 41.0mg,93％yield,white solid,mp＝98-99℃,
Figure BDA0002401340770000113
MHz,CDCl3)δ142.8,140.0,127.2,126.9,79.9,35.4,19.1,18.4.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.7mL/min,retention time 9.6min,12.9min(meso)and 21.6min(major).
HRMS:Calculated for C20H27O2[M+H]+299.2006,found:299.1991.
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(pentan-1-ol)(4ca-4):Thereaction was conducted by using polysilyether 3ca-4(77.4mg,0.15mmol),affording 4ca-4 44.8mg,91％yield,white solid,mp＝120-121℃,
Figure BDA0002401340770000114
CDCl3)δ144.1,140.2,127.2,126.5,74.6,38.9,28.2,22.8,14.2.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.7mL/min,retention time 8.0min,10.8min(meso)and 15.7min(major).HRMS:Calculated for C22H30O2Na[M+Na]+349.2138,found:349.2138.
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(3-methylbutan-1-ol)(4ca-5):The reaction was conducted by using polysilyether 3ca-5(77.4mg,0.15mmol),affording 4ca-5 41.4mg,81％yield,white solid,mp＝108-109
Figure BDA0002401340770000115
1.62-1.45(m,2H),1.05-0.84(m,12H).13C NMR(100MHz,CDCl3)δ144.4，140.1，127.2，126.5，72.6，48.5，24.9，23.3,22.4.HPLC:Chiracel IA column,254nm,30℃,n-Hexane/i-PrOH＝90/10,flow＝0.7mL/min,retention time 23.2min,28.9min(major)and 31.5min(meso).HRMS:Calculated for C22H30O2Na[M+Na]+349.2138,found:349.2133.
(1R,1'R)-[1,1'-biphenyl]-4,4'-diylbis(phenylmethanol)(4ca-6)::Thereaction was conducted by using polysilyether 3ca-6(83.4mg,0.15mmol),affording 4ca-6 50.3mg,92％yield,white solid,known compound[8],
Figure BDA0002401340770000116
127.1,126.7,76.17.HPLC:Chiracel IC column,254nm,30℃,n-Hexane/i-PrOH＝80/20,flow＝0.7mL/min,retention time 18.4min(meso),19.9min(major)and 23.3min.
(1R,1'R)-1,1'-([1,1'-biphenyl]-4,4'-diyl)bis(3-phenylpropan-1-ol)(4ca-7):The reaction was conducted by using polysilyether 3ca-7(92.0mg,0.15mmol),affording 4ca-7 60.4mg,95％yield,white solid,new compound,
Figure BDA0002401340770000121
143.8,141.9,140.3,128.59,128.56,127.3,126.6,126.0,73.8,40.6,32.2.HPLC:Chiracel IC column,254nm,30℃,n-Hexane/i-PrOH＝80/20,flow＝0.7mL/min,retention time 15.8min(major),17.1min(meso)and 22.9min.HRMS:Calculatedfor C30H30O2Na[M+Na]+445.2138,found:445.2138.(1R,1'R)-1,1'-([1,1'-biphenyl]-3,3'-diyl)bis(ethan-1-ol)(4cb):The reaction was conducted by usingpolysilyether 3cb(57.1mg,0.13mmol),affording 4cb 29.1mg,91％yield,whitesolid,known compound[9],99％
Figure BDA0002401340770000122
124.6,124.4,70.6,25.4.HPLC:Chiracel OJ-H column,254nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.8mL/min,retention time 6.2min,8.7min(meso)and 10.8min(major).
(1R,1'R)-1,1'-(methylenebis(4,1-phenylene))bis(ethan-1-ol)(4cc):Thereaction was conducted by using polysilyether 3cc(66.9mg,0.15mmol),affording4cc 20.3mg,53％yield,white solid,known compound[10],99％
Figure BDA0002401340770000123
25.2.HPLC:Chiracel OD-H column,230nm,30℃,n-Hexane/i-PrOH＝80/20,flow＝0.7mL/min,retention time 11.6min(major),13.1min(meso)and 14.5min.
(1R,1'R)-1,1'-(1,4-phenylene)bis(ethan-1-ol)(4cg):The reaction wasconducted by using polysilyether 3cg(116.0mg,0.33mmol),affording 4cg 35.2mg,64％yield,white solid,known compound[11],99％ee,94:6 dr.1H
Figure BDA0002401340770000124
column,254nm,30℃,n-Hexane/i-PrOH＝95/5,flow＝0.7mL/min,retention time 50.8min(major),61.2min and 86.2min(meso).
(1R,1'R)-1,1'-(1,3-phenylene)bis(ethan-1-ol)(4cf):The reaction wasconducted by using polysilyether 3cf(56.1mg,0.16mmol),affording 4cf 22.0mg,84％yield,white solid,known compound[11],98.2％ee,90:10 dr.
Figure BDA0002401340770000125
retention time 23.7min,30.1min(meso)and 35.4min(major).
(1R,5R)-1,5-diphenylpentane-1,5-diol(4ch):The reaction was conductedby using polysilyether 3ch(66.9mg,0.15mmol),affording 4ch 27.3mg,71％yield,white solid,known compound[12],98％ee,83:17dr.1H NMR(400
Figure BDA0002401340770000126
30℃,n-Hexane/i-PrOH＝80/20,flow＝0.7mL/min,retention time 12.2min(major),13.7min(meso)and 18.1min.
(1R,1'R)-1,1'-([2,2'-bithiophene]-5,5'-diyl)bis(ethan-1-ol)(4ce):Thereaction was conducted by using polysilyether 3ce(48.2mg,0.11mmol),affording4ce 23.1mg,91％yield,white solid,mp＝109-110℃,new
Figure BDA0002401340770000127
6H).13CNMR(100MHz,CDCl3)δ149.0，136.7，124.0，123.3，66.5，25.3.HPLC:Chiracel IC column,254nm,30℃,n-Hexane/i-PrOH＝75/25,flow＝0.7mL/min,retention time 15.1min,17.0min(meso)and 18.4min(major).HRMS:Calculated for C12H14O2S2Na[M+Na]+277.0327,found:277.0324.
(1R,1'R)-1,1'-(pyridine-2,6-diyl)bis(ethan-1-ol)(4ci):The reactionwas conducted by using polysilyether 3ci(147.0mg,0.41mmol),affording 4ci55.9mg,82％yield,colorless oil,known compound[13],98.4％ee,90:10
Figure BDA0002401340770000131
n-Hexane/i-PrOH＝95/5,flow＝0.8mL/min,retention time 18.3min(major),21.4min and23.8min(meso).

Claims (6)

1.一种手性聚硅醚的合成方法，其特征在于，所述手性聚硅醚包括式(Ⅰ)或式(Ⅱ)所示具有硅氧键结构的重复单元：
Figure FDA0003744639360000011
其中，R1为-O-、
Figure FDA0003744639360000012
R2为
Figure FDA0003744639360000013
Figure FDA0003744639360000014
R3为-Ph或-Me；
R4为甲基、乙基、丙基、异丙基、正丁基、异丁基或芳基；
所述手性聚硅醚的ee值为98％～99.8％；
所述合成方法以[Cu]为前体，以铜氢双膦配体L为催化剂，在有机溶剂中，实现硅烷单体和二酮单体的不对称硅氢化聚合，形成具有硅氧键结构的手性聚硅醚；
所述[Cu]为叔丁醇亚铜、醋酸铜、环己丁酸铜、醋酸亚铜中的至少一种；
所述铜氢双膦配体L为L1～L4中的一种：
Figure FDA0003744639360000015
所述硅烷单体为1a-1e中的一种：
Figure FDA0003744639360000021
所述二酮单体为2a-2i中的一种：
Figure FDA0003744639360000022
其中，R4为甲基、乙基、丙基、异丙基、正丁基、异丁基、芳基中的一种。
2.根据权利要求1所述的合成方法，其特征在于，所述有机溶剂为甲苯、甲基叔丁基醚、四氢呋喃、1,4-二氧六环、均三甲苯中的至少一种。
3.根据权利要求1或2所述的合成方法，其特征在于，所述合成方法的具体步骤为：
在氮气保护下，向封管中加入[Cu]、铜氢双膦配体L和有机溶剂，于室温搅拌反应0.5-2h后，氮气保护下加入硅烷单体和二酮单体，于30-80℃搅拌反应24-48h后，旋干溶剂，用二氯甲烷、甲醇按体积比为0.5:5-0.5:10沉淀聚合物，沉淀分离得到手性聚硅醚产物。
4.根据权利要求3所述的合成方法，其特征在于，所述[Cu]、铜氢双膦配体L、硅烷单体、二酮单体的摩尔比为：0.005～0.025:0.005～0.025:1:1。
5.根据权利要求3所述的合成方法，其特征在于，所述硅烷单体和二酮单体在溶剂中的浓度分别为0.1～1.0mmol/mL。
6.权利要求1-5中任一项所述的合成方法合成的手性聚硅醚在不对称催化、手性分离中的应用。
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