CN108440591B - 一种手性二氢硅烷化合物的合成方法 - Google Patents

一种手性二氢硅烷化合物的合成方法 Download PDF

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CN108440591B
CN108440591B CN201810229724.1A CN201810229724A CN108440591B CN 108440591 B CN108440591 B CN 108440591B CN 201810229724 A CN201810229724 A CN 201810229724A CN 108440591 B CN108440591 B CN 108440591B
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陆展
程彪
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Abstract

本发明公开了一种手性二氢硅烷化合物的合成方法：以式I所示的烯烃和式II所示的硅烷为原料，手性FeX2‑OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物；手性FeX2‑OIP络合物为式III所示的化合物或其对映体。本发明方法提供了一种有效的由手性FeX2‑OIP络合物为催化剂，由烯烃和硅烷高效率高对映体选择性的合成光学活性的硅烷化合物的方法。反应的产率较好，一般为56％～97％，对映体选择性比CoX2‑OIP络合物催化剂显著提高，特别对于脂肪族烯烃的底物，ee值可达97％～>99％。
Figure DDA0001602245250000011

Description

一种手性二氢硅烷化合物的合成方法
技术领域
本方法涉及一种手性二氢硅烷化合物的合成方法，尤其是涉及一种光学活性的硅烷化合物的合成方法。
背景技术
烯烃的不对称转化是构建手性分子最有效的方法之一，已经被广泛应用于工业和学术界(Kolb,H.C.；VanNieuwenhze,M.S.；Sharpless,K.B.Chem.Rev.1994, 94,2483)。然而，对于工业易得的非活化末端烯烃，却很少被应用在催化不对称转化中(Coombs,J.R.；Morken,J.P.Angew.Chem.Int.Ed.2016,55,2636)。出现这种情况的原因主要有一下三点。第一，非活化烯烃含有很少的电子效应，没有螯和基团和导向基团，这导致了在控制区域选择性上的困难。第二，简单末端烯烃的两个潜手性面很难区分，这导致了控制立体选择性上的困难。第三，催化活性中间体更容易和官能团而不是简单烯烃反应，这导致了在成功的例子中官能团容忍性都非常局限。因此，发展高区域选择性、高对映选择性、良好的官能团容忍性的简单易得的非活化烯烃的硅氢化反应非常有意义。
手性有机硅烷在有机合成、硅材料、硅代药物等领域有些十分广泛的应用。烯烃的不对称硅氢化是合成手性有机硅烷的重要途径，但是脂肪族烯烃的硅氢化依然是一个很大的挑战。在1991年，Hayashi课题组报道了首例成功的钯催化的不对称脂肪族末端烯烃的硅氢化反应(Uozumi,Y.；Hayashi,T.J.Am.Chem.Soc. 1991,113,9887)。该反应以优秀的对映选择性(高达97％ee)和中等至良好的区域选择性(66/34–94/6b/l)得到手性有机硅烷。此后，很多课题组尝试使用贵金属和手性膦配体来提高这一反应的结果，但到目前为止还没有更好的结果报道出来。与此同时，反应中用到的比较活泼的HSiCl3也使得底物范围非常局限。在2017年，陆展课题组报道了钴催化的烯烃的马氏硅氢化反应，但是对于脂肪族烯烃的底物，对映选择性最高只能达到88％ee(Cheng,B.；Lu,P.；Zhang,H.-Y.； Cheng,X.-P.；Lu,Z.J.Am.Chem.Soc.2017,139,9439)，手性产物的纯度有待进一步提高。
铁，作为一种地球丰产、无毒、廉价、生物兼容性好的过渡金属，在很多领域中有些非常大的吸引力。然而，到目前为止，铁催化的脂肪族烯烃的不对称马氏硅氢化依然是一个很大的挑战，即使是外消的反应依然还没有报道。
因此，发展铁催化的高对映选择性、高区域选择性、良好官能团容忍性的脂肪族末端烯烃的硅氢化反应有些十分重要的意义。
发明内容
本发明要解决的问题是提供一种基于简单烯烃有效合成手性二氢硅烷化合物的方法，是由手性FeX2-OIP络合物(OIP：亚胺吡啶噁唑啉配体)催化烯烃和硅烷的硅氢化反应，高效率高对映体选择性地合成光学活性的二氢硅烷化合物的方法。
本发明是通过以下技术方案来实现的：
一种手性二氢硅烷化合物的合成方法，所述方法包括以下步骤：
以式I所示的烯烃和式II所示的硅烷为原料，手性FeX2-OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物；
Figure BDA0001602245230000021
式IV中，*代表手性碳原子；
式I、式II或式IV中，R1,R2任选自C1-C16的烷基、C3-C16的环烷基、式V 所示的基团或C4～C10的含N、O、S的杂环芳基；所述烷基、环烷基上的H不被取代或被1个以上的取代基A取代，所述取代基A包括苯基、萘基、萘基甲氧基、杂环芳基、杂环芳基甲氧基、C1-C16的硅烷基、C1-C16的硅氧基、C1-C16的磺酰氧基、卤素、苄氧基、C1-C16的烷氧基、C1-C16的酯基、C1-C16的缩酮基、邻苯二甲酰亚胺基、环己胺基、C1-C16的烯基或C1-C16的烯基甲氧基；所述杂环芳基包括吲哚基、吡啶基、噻吩基或呋喃基；所述杂环芳基甲氧基包括吲哚基甲氧基、吡啶基甲氧基、噻吩基甲氧基或呋喃基甲氧基；
Figure BDA0001602245230000022
式V中，R3、R4、R5、R6、R7任选自H、卤素、C1-C16的烷基、C1-C16的烷氧基、C1-C16的烷硫基、苯基、三氟甲基、甲氧羰基、硝基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3- 二氧环戊基中的任意一种。卤素包括F、Cl、Br或I；R3，R4，R5，R6,R7全为H 时，式V所示的基团即为苯基。
进一步，优选所述R1为C1-C16的烷基，所述烷基的H不被取代或被1个以上的取代基A取代，所述取代基A包括苯基、三甲基硅基、卤素、叔丁基二甲基硅氧基、甲基磺酰氧基、对甲苯磺酰氧基、苄氧基、乙酰氧基、2-甲基-1,3-二氧 -2-环戊基、邻苯二甲酰亚胺基、环己胺基、哌啶基、α-苯乙烯基、β-苯乙烯基、β-苯乙烯基甲氧基、萘基、吲哚基、吡啶基、噻吩基、呋喃基、萘基甲氧基、吡啶甲基氧基、呋喃甲基氧基、噻吩甲基氧基；2-甲基-6-甲氧基-2-萘乙酸酯基、2-(4-异丁基苯基)丙酸酯基或苯硅基
优选R2为式V所示的基团；
式V所示的基团优选为苯基或含有1～2个以下取代基的取代苯基：甲基、丁基、苯基、甲氧基、甲硫基、F、Cl、Br、三氟甲基、甲氧羰基、乙酰氧甲基、 2-甲基-1,3-二氧环戊基。
更优选R2为苯基、对甲氧基苯基或对氯苯基。
更进一步，优选所述R1为RA—(CH2)n—，n为1～16的整数，RA为碳链上的取代基，RA包括苯基、三甲基硅基、卤素、叔丁基二甲基硅氧基、甲基磺酰氧基、对甲苯磺酰氧基、苄氧基、乙酰氧基、2-甲基-1,3-二氧-2-环戊基、邻苯二甲酰亚胺基、环己胺基、哌啶基、α-苯乙烯基、β-苯乙烯基、β-苯乙烯基甲氧基、萘基、吲哚基、吡啶基、噻吩基、呋喃基、萘基甲氧基、吡啶甲基氧基、呋喃甲基氧基、噻吩甲基氧基；2-甲基-6-甲氧基-2-萘乙酸酯基、2-(4-异丁基苯基)丙酸酯基或苯硅基
本发明所用的催化剂为手性FeX2-OIP络合物(OIP：亚胺吡啶噁唑啉配体)，结构式为式III所示的化合物或其对映体，所述对映体即为式III的镜像。R8， R9,R10,R11,R12,R13,R14,R15,R16,R17,R18,R19任选自H、C1-C16的烷基、C1-C16的烷氧基、苯基、萘基、或苄基：所述烷基、烷氧基上的H不被取代或被1个以上的取代基C取代，所述取代基C包括硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；所述苯基、苄基、萘基上的H不被取代或被1个以上的取代基D取代，所述取代基D包括C1～ C3的烷基、C1～C3的烷氧基、硝基、卤素、苯基、甲氧羰基、三氟甲基、羟基、 C1～C3的醛基、C1～C3的羧基、氨基、C1～C3的酯基或酰胺基；X为F、Cl、Br、I、 OAc、CF3SO3中的任意一种。
Figure BDA0001602245230000041
进一步，式III中，优选R8为C1-C4的烷基，更优选为异丙基、R9为C1-C4的烷基或二苯基次甲基，R10为H，R11为C1-C4的烷基、C1-C4的烷氧基或卤素； R12为H；R13为C1-C4的烷基或二苯基次甲基；R14为甲基；R15、R16、R17、R18、 R19均为H。
更优选的，所用的催化剂如式III-1所示
Figure BDA0001602245230000042
式III-1中，iPr代表异丙基，Ph代表苯基，MeO代表甲氧基；
本发明合成方法的反应式如下所示
Figure BDA0001602245230000043
作为进一步地改进，本发明所述的合成方法可在有机溶剂中进行，所述的有机溶剂可以为苯、四氯化碳、甲苯、四氢呋喃、乙醚、二氯甲烷、乙腈、二氧六环、石油醚、环己烷、正己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种，优选四氢呋喃。
所述有机溶剂的体积用量一般以式I所示的烯烃的物质的量计为 1～10mL/mmol。
作为进一步地改进，本发明所述的式I所示的烯烃、式II所示的硅烷、手性 FeX2-OIP络合物、还原剂的物质的量之比为1：0.1-10：0.0000005-0.05： 0.0000005-0.15，优选为1：0.1-10：0.0005-0.05：0.0015-0.15，更优选为1：0.5-2： 0.001-0.05：0.001-0.15；最优选为1：1～1.2：0.02：0.06。
作为进一步地改进，本发明所述的所述合成方法中，反应温度为-30℃～ 80℃，优选-10℃～60℃，尤其推荐0℃。
本发明反应的反应时间优选3分钟-48小时，优选为30分钟-12小时，尤其推荐2小时
本发明的还原剂为三乙基硼氢化钠、三仲丁基硼氢化钠、三乙基硼氢化锂、叔丁醇钠、叔丁醇钾、叔丁醇锂、叔戊醇钠、乙醇钠、甲醇钠、甲醇钾中的任意一种，优选三乙基硼氢化钠、叔丁醇钠、乙醇钠、甲醇钠，更优选为叔丁醇钠。
作为进一步地改进，本发明反应结束后，所得粗产物经过后处理制得式IV 所示的手性二氢硅烷化合物，进一步，所述后处理方法为下列一种或两种以上：重结晶、薄层层析、柱层析或减压蒸馏，优选为柱层析。
本发明方法提供了一种有效的由手性FeX2-OIP络合物为催化剂，由烯烃和硅烷高效率高对映体选择性的合成光学活性的硅烷化合物的方法。与现有方法相比，该方法适用于多种不同类型的烯烃，反应条件温和，操作简便，原子经济性高。另外，反应无需其他任何的有毒过渡金属(如钌、铑、钯等)盐类的加入，在药物和材料合成上具有较大的实际应用价值。且反应的产率也较好，一般为 56％～97％，对映体选择性比CoX2-OIP络合物催化剂显著提高，特别对于脂肪族烯烃的底物，ee值可达97％～>99％。
本发明方法制得的式IV所示的手性二氢硅烷化合物可用于氧化合成手性醇类化合物，手性硅醇类化合物等。二氢硅烷化合物用于合成醇类化合物、硅醇类化合物属于公知的方法，本发明合成出来的手性二氢硅烷同样适用这些方法，因此本申请的手性二氢硅烷可进一步用于光学活性的简单脂肪醇或硅醇化合物的合成，具有较大的应用价值。
Figure BDA0001602245230000061
附图说明
图1催化剂手性FeX2-OIP络合物III-1的单晶结构图。
具体实施方式
下面通过具体实施例对本发明的技术方案作进一步地具体说明，但本发明的保护范围不限于此：
实施例1：手性FeX2-OIP络合物催化的烯烃和硅烷的硅氢化反应
室温下，在一干燥的反应试管中加入手性FeX2-OIP络合物(0.02mmol)，式I所示的烯烃(1.0mmol)，式II所示的硅烷(1.2mmol)，四氢呋喃(1mL)，然后置于冰水浴中并加入叔丁醇钠(0.06mmol)，0℃下搅拌2小时后柱层析分离(洗脱溶剂为石油醚或石油醚和乙酸乙酯的混合物)得到产物。
实施例1中，手性FeX2-OIP络合物的化学式如下式III-1所示：
Figure BDA0001602245230000062
其制备方法如下(Chen,J.；Cheng,B.；Cao,M.；Lu,Z.Angew.Chem.Int.Ed. 2015,54,4661-4664)：在氮气保护下，向干燥的Schlenk管中加入式VI所示的 OIP配体(Cheng,B.；Lu,P.；Zhang,H.；Cheng,X.；Lu,Z.J.Am.Chem.Soc.2017, 139,9439-9442.)(1.5391g,2.3mmol)，THF(30mL)，FeCl2(0.2622g, 2.1mmol)。反应混合物在25℃下搅拌4h后，注射30mL乙醚进入反应混合物，继续搅拌2h。反应混合物过滤，固体用乙醚(50mL)洗涤，在真空下干燥，得到绿色粉末(1.5267g,1.9mmol,33％产率)。
III-1的单晶结构如图1所示，CCDC号：1813349
IV-1:(S)-5-(phenylsilyl)hexyl methanesulfonate.
(S)-(5-苯硅基己基)甲磺酸酯
Figure 1
4.26-4.16(m,4H),2.98(s,3H),1.79-1.66(m,2H),1.59-1.49(m,2H),1.46-1.30(m, 2H),1.20-1.10(m,1H),1.07(d,J＝6.4Hz,3H)；13C NMR(CDCl3,100MHz):δ135.5, 131.7,129.5,127.9,69.9,37.2,32.7,29.0,24.3,16.1,15.9；HRMS(ESI)calculated for[C13H22O3SSiNa]+(M+Na+)requires m/z 309.0957,found m/z 309.0958.
IV-2:(S)-hexan-2-yl(phenyl)silane.
(S)-2-苯硅基己烷
Figure BDA0001602245230000072
4.26-4.15(m,2H),1.53-1.20(m,6H),1.19-1.08(m,1H),1.06(d,J＝6.8Hz,3H), 0.87(t,J＝6.8Hz,3H)；13C NMR(CDCl3,100MHz):δ135.6,132.3,129.4,127.9, 33.1,30.8,22.7,16.2,16.1,14.0；HRMS(ESI)calculated for[C12H21Si]+(M+H+) requires m/z 193.1413,found m/z 193.1417.
IV-3:(S)-octan-2-yl(phenyl)silane.
(S)-2-苯硅基辛烷
Figure BDA0001602245230000073
J＝7.2Hz,3H),0.87(t,J＝6.8Hz,3H)；These spectroscopic data are correspondingto the previously reported data.(Cheng,B.；Lu,P.；Zhang,H.；Cheng,X.；Lu,Z.J.Am.Chem.Soc.2017,139,9439-9442.)
IV-4:(S)-dodecan-2-yl(phenyl)silane.
(S)-2-苯硅基十二烷
Figure BDA0001602245230000074
4.48-3.92(m,2H),1.52-1.18(m,18H),1.18-1.08(m,1H),1.05(d,J＝6.8Hz,3H), 0.88(t,J＝6.4Hz,3H)；13C NMR(CDCl3,100MHz):δ135.6,132.3,129.4,127.9, 33.5,31.9,29.70,29.66,29.65,29.58,29.4,28.6,22.7,16.3,16.1,14.1；HRMS(ESI) calculated for[C18H33Si]+(M+H+)requires m/z 277.2352,found m/z 277.2366.
IV-5:(S)-(4-methylpentan-2-yl)(phenyl)silane.
(S)-(1,3-二甲基丁基)苯基硅烷
Figure BDA0001602245230000075
IR(neat,cm-1):2956,2924,2854,2132,1463,1378.1H NMR(CDCl3,400MHz): δ7.60-7.53(m,2H),7.43-7.32(m,3H),4.48-3.92(m,2H),1.79-1.66(m,1H), 1.36-1.16(m,3H),1.03(d,J＝6.8Hz,3H),0.88(d,J＝6.4Hz,3H),0.84(d,J＝6.8 Hz,3H)；13C NMR(CDCl3,100MHz):δ135.7,132.2,129.5,127.9,42.6,25.9,23.1, 21.8,16.0,13.7；HRMS(EI)calculated for[C12H20Si]+requires m/z 192.1334,found m/z 192.1331.
IV-6:(S)-phenyl(1-phenylpropan-2-yl)silane.
(S)-1-苯基-2-苯硅基丙烷
Figure BDA0001602245230000081
NMR(CDCl3,400MHz):δ7.62-7.53(m,2H),7.45-7.33(m,3H),7.31-7.23(m,2H), 7.22-7.11(m,3H),4.51-3.95(m,2H),2.90(dd,J＝5.2,13.6Hz,1H),2.49(dd,J＝ 10.4,13.6Hz,1H),1.52-1.41(m,1H),1.01(d,J＝7.2Hz,3H)；13C NMR(CDCl3,100 MHz):δ141.5,135.6,131.7,129.6,128.9,128.1,127.9,125.8,39.4,18.5,15.5； HRMS(EI)calculated for[C15H18Si]+requires m/z 226.1178,found m/z 226.1180.
IV-7:(S)-trimethyl(2-(phenylsilyl)propyl)silane.
(S)-三甲基(2-苯硅基丙基)硅烷
Figure BDA0001602245230000082
4.48-3.91(m,2H),1.31-1.19(m,1H),1.09(d,J＝7.6Hz,3H),0.80(dd,J＝4.0,14.8 Hz,1H),0.49(dd,J＝10.0,14.8Hz,1H),0.01(s,9H).These spectroscopic data arecorresponding to the previously reported data.(Cheng,B.；Lu,P.；Zhang,H.；Cheng,X.；Lu,Z.J.Am.Chem.Soc.2017,139,9439-9442.)
IV-8:(S)-(6-chlorohexan-2-yl)(phenyl)silane(3h).
(S)-1-氯-2-苯硅基己烷
Figure BDA0001602245230000083
4.50-3.94(m,2H),3.51(t,J＝6.8Hz,2H),1.80-1.69(m,2H),1.63-1.30(m,4H), 1.20-1.10(m,1H),1.07(d,J＝6.8Hz,3H)；13C NMR(CDCl3,100MHz):δ135.6, 131.8,129.5,127.9,44.9,32.6,25.7,16.1,16.0；HRMS(ESI)calculated for [C12H20ClSi]+(M+H+)requires m/z 227.1023,found m/z 227.1012.
IV-9:(S)-tert-butyldimethyl((5-(phenylsilyl)hexyl)oxy)silane.
(S)-1-(叔丁基二甲基硅氧基)-2-苯硅基己烷
Figure BDA0001602245230000084
4.49-3.93(m,2H),3.58(t,J＝6.0Hz,2H),1.54-1.41(m,4H),1.40-1.30(m,2H), 1.20-1.09(m,1H),1.06(d,J＝7.2Hz,3H),0.89(s,9H),0.04(s,6H)；13C NMR (CDCl3,100MHz):δ135.6,132.1,129.5,127.9,63.1,33.2,32.9,26.0,24.7,18.3, 16.3,16.0,-5.3；HRMS(ESI)calculated for[C18H35OSi2]+(M+H+)requires m/z 323.2226,found m/z 323.2231.
IV-10:(S)-5-(phenylsilyl)hexyl 4-methylbenzenesulfonate.
(S)-(5-苯硅基己基)对甲苯磺酸酯
Figure BDA0001602245230000091
2H),7.43-7.31(m,5H),4.22-4.12(m,2H),4.00(t,J＝6.4Hz,2H),2.45(s,3H), 1.68-1.53(m,2H),1.48-1.38(m,2H),1.37-1.20(m,2H),1.13-0.98(m,4H)；13C NMR(CDCl3,100MHz):δ144.4,135.2,132.8,131.3,129.5,129.3,127.7,127.5, 70.2,32.3,28.5,23.9,21.2,15.7,15.6；HRMS(EI)calculated for [C19H25O3SSi]+(M-H+)requires m/z 361.1294,found m/z 361.1299.(相应外消产物为已知化合物：Du,X.-Y.；Zhang,Y.-L.；Peng,D.-J.；Huang,Z.Angew.Chem.Int. Ed.2016,55,6671.)
IV-11:(S)-(6-(benzyloxy)hexan-2-yl)(phenyl)silane.
(S)-1-苄氧基-2-苯硅基己烷
Figure BDA0001602245230000092
4.49(s,2H),4.25-4.16(m,2H),3.44(t,J＝6.0Hz,2H),1.66-1.46(m,4H),1.45-1.29 (m,2H),1.19-1.09(m,1H),1.06(d,J＝6.8Hz,3H)；13C NMR(CDCl3,100MHz): δ138.6,135.5,132.0,129.4,128.3,127.8,127.5,127.4,72.8,70.2,33.2,29.7,25.1, 16.2,16.0；HRMS(EI)calculated for[C19H26OSi]+requires m/z 298.1753,found m/z 298.1757.
IV-12:(S)-5-(phenylsilyl)hexyl acetate.
(S)-(5-苯硅基己基)乙酸酯
Figure BDA0001602245230000093
4.26-4.16(m,2H),4.03(t,J＝6.8Hz,2H),2.04(s,3H),1.66-1.42(m,4H),1.41-1.31 (m,2H),1.20-1.10(m,1H),1.06(d,J＝7.2Hz,3H)；13C NMR(CDCl3,100MHz): δ171.0,135.5,131.8,129.5,127.9,64.3,32.9,28.5,24.8,20.9,16.1,15.9；HRMS(EI) calculated for[C14H21O2Si]+(M-H+)requires m/z 249.1311,found m/z 249.1312.(相应外消产物为已知化合物：Du,X.-Y.；Zhang,Y.-L.；Peng,D.-J.；Huang,Z.Angew. Chem.Int.Ed.2016,55,6671.)
IV-13:(S)-(4-(2-methyl-1,3-dioxolan-2-yl)butan-2-yl)(phenyl)silane.
5-苯硅基-2-己酮缩乙二醇
Figure BDA0001602245230000094
4.28-4.17(m,2H),3.98-3.85(m,4H),1.84-1.74(m,1H),1.71-1.59(m,2H), 1.49-1.37(m,1H),1.29(s,3H),1.18-1.03(m,4H)；13C NMR(CDCl3,100MHz): δ135.6,131.8,129.5,127.9,110.0,64.5,38.0,27.6,23.6,16.4,16.1；HRMS(ESI) calculated for[C14H22O2SiNa]+(M+Na+)requires m/z 273.1287,found m/z 273.1299. (相应外消产物为已知化合物：Du,X.-Y.；Zhang,Y.-L.；Peng,D.-J.；Huang,Z. Angew.Chem.Int.Ed.2016,55,6671.)
IV-14:(S)-2-(10-(phenylsilyl)undecyl)isoindoline-1,3-dione.
(S)-N-(10-苯硅基十一烷基)-邻苯二甲酰胺
Figure BDA0001602245230000101
14H),1.17-0.98(m,4H)；These spectroscopic data are corresponding to thepreviously reported data.(Cheng,B.；Lu,P.；Zhang,H.；Cheng, X.；Lu,Z.J.Am.Chem.Soc.2017,139,9439-9442.)
IV-15:(S)-1-(5-(phenylsilyl)hexyl)piperidine.
(S)-N-(5-苯硅基己基)哌啶
Figure BDA0001602245230000102
4.48-3.92(m,2H),2.44-2.18(m,6H),1.64-1.24(m,12H), 1.20-1.08(m,1H),1.05(d,J＝6.8Hz,3H)；13C NMR(CDCl3,100MHz):δ135.5, 132.0,129.4,127.8,59.4,54.5,33.2,26.8,26.5,25.9,24.4,16.1,16.0；HRMS(EI) calculated for[C17H29NSi]+requires m/z275.2069,found m/z 275.2074.
IV-16:(S)-phenyl(5-phenylhex-5-en-2-yl)silane.
(S)-1-(3-苯硅基丁基)-1-苯基乙烯
Figure BDA0001602245230000103
1H),5.03(d,J＝0.8Hz,1H),4.50-3.94(m,2H),2.70-2.47(m,2H), 1.75-1.62(m,1H),1.53-1.42(m,1H),1.27-1.15(m,1H),1.09(d,J＝6.8Hz,3H)；13C NMR(CDCl3,100MHz):δ148.4,141.1,135.6,131.8,129.5,128.2,127.9,127.3, 126.1,112.4,34.2,32.1,16.1,15.8；HRMS(EI)calculated for[C18H22Si]+requires m/z 266.1491,found m/z 266.1491.
IV-17:(S,E)-(6-(cinnamyloxy)hexan-2-yl)(phenyl)silane.
(S,E)-1-苯基-2-(5-苯硅基己氧基)甲基乙烯
Figure BDA0001602245230000104
7H),7.26-7.17(m,1H),6.60(d,J＝16.0Hz,1H),6.29(dt,J＝6.0,16.0Hz,1H), 4.26-4.17(m,2H),4.12(d,J＝6.0Hz,2H),3.45(t,J＝6.4Hz,2H),1.66-1.48(m, 4H),1.46-1.29(m,2H),1.20-1.10(m,1H),1.06(d,J＝7.2Hz,3H)；13C NMR(CDCl3, 100MHz):δ136.7,135.6,132.0,129.4,128.5,127.9,127.5,126.4,71.3,70.3,33.2, 29.8,25.1,16.2,16.0；HRMS(ESI)calculated for[C21H29OSi]+(M+H+)requires m/z 325.1988,found m/z 325.1998.
IV-18:(S)-(6-(naphthalen-2-ylmethoxy)hexan-2-yl)(phenyl)silane.
(S)-2-(5-苯硅基己氧基)甲基萘
Figure BDA0001602245230000111
3H),7.77(s,1H),7.57-7.52(m,2H),7.50-7.43(m,3H), 7.41-7.30(m,3H),4.65(s,2H),4.48-3.93(m,2H),3.49(t,J＝6.4Hz,2H),1.69-1.57 (m,2H),1.57-1.48(m,2H),1.47-1.30(m,2H),1.20-1.09(m,1H),1.06(d,J＝7.2Hz, 3H)；13C NMR(CDCl3,100MHz):δ136.2,135.6,133.3,132.9,132.0,129.5,128.1, 127.9,127.8,127.6,126.2,126.0,125.7,72.9,70.3,33.2,29.8,25.1,16.2,16.0； HRMS(ESI)calculated for[C23H28OSiNa]+(M+Na+)requires m/z 371.1807,found m/z 371.1803.
IV-19:(S)-1-(5-(phenylsilyl)hexyl)-1H-indole.
(S)-N-(5-苯硅基己基)吲哚
Figure BDA0001602245230000112
7.55-7.49(m,2H),7.42-7.28(m,4H),7.19(dd,J＝7.6,7.2Hz, 1H),7.09(dd,J＝7.2,7.2Hz,1H),7.05(d,J＝3.2Hz,1H),6.47(d,J＝3.2Hz,1H), 4.22-4.14(m,2H),4.07(t,J＝7.2Hz,2H),1.87-1.74(m,2H),1.57-1.40(m,2H), 1.40-1.27(m,2H),1.16-1.06(m,1H),1.03(d,J＝6.8Hz,3H)；13C NMR(CDCl3,100 MHz):δ135.9,135.5,131.8,129.5,128.6,127.9,127.7,121.2,120.9,119.1,109.3, 100.8,46.1,32.9,30.1,25.8,16.1,16.0；HRMS(ESI)calculated for [C20H26NSi]+(M+H+)requires m/z 308.1835,found m/z 308.1833.
IV-20:(S)-2-(((5-(phenylsilyl)hexyl)oxy)methyl)pyridine.
(S)-2-(5-苯硅基己氧基)甲基吡啶
Figure BDA0001602245230000113
Hz,1H),7.73-7.65(m,1H),7.56(dd,J＝1.2,7.6Hz,2H),7.44(d,J＝8.0Hz,1H), 7.40-7.32(m,3H),7.18(dd,J＝4.8,6.8Hz,1H),4.62(s,2H),4.49-3.93(m,2H), 3.54(t,J＝6.4Hz,2H),1.70-1.59(m,2H),1.58-1.49(m,2H),1.48-1.31(m,2H), 1.20-1.10(m,1H),1.06(d,J＝7.2Hz,3H)；13C NMR(CDCl3,100MHz):δ158.7, 148.8,136.4,135.4,131.8,129.3,127.7,122.0,121.0,73.5,70.8,33.1,29.6,24.9, 16.1,15.9；HRMS(ESI)calculated for[C18H26NOSi]+(M+H+)requires m/z 300.1784, found m/z 300.1795.
IV-21:(S)-(6-(furan-2-ylmethoxy)hexan-2-yl)(phenyl)silane.
(S)-2-(5-苯硅基己氧基)甲基呋喃
Figure BDA0001602245230000121
4H),6.36-6.27(m,2H),4.42(s,2H),4.25-4.15(m,2H),3.44(t,J＝6.4Hz,2H), 1.64-1.42(m,4H),1.42-1.24(m,2H),1.18-1.07(m,1H),1.05(d,J＝7.2Hz,3H)；13C NMR(CDCl3,100MHz):δ152.1,142.6,135.6,132.0,129.4,127.9,110.1,108.9, 70.1,64.7,33.1,29.6,25.0,16.2,16.0；HRMS(ESI)calculated for [C17H24O2SiNa]+(M+Na+)requires m/z311.1443,found m/z 311.1449.
IV-22:(S)-phenyl(6-(thiophen-2-ylmethoxy)hexan-2-yl)silane.
(S)-2-(5-苯硅基己氧基)甲基噻吩
Figure BDA0001602245230000122
7.29-7.24(m,1H),7.00-6.94(m,2H),4.64(s,2H),4.47-3.92(m,2H),3.45(t,J＝ 6.4Hz,2H),1.65-1.45(m,4H),1.44-1.27(m,2H),1.19-1.08(m,1H),1.05(d,J＝7.2 Hz,3H)；13CNMR(CDCl3,100MHz):δ141.5,135.6,132.0,129.4,127.8,126.5, 126.0,125.5,69.9,67.2,33.1,29.6,25.0,16.2,16.0；HRMS(ESI)calculated for [C17H24OSSiNa]+(M+Na+)requires m/z 327.1215,found m/z 327.1221.
IV-23:(S)-(S)-5-(phenylsilyl)hexyl 2-(6-methoxynaphthalen-2-yl)propanoate.
(S)-(S)-2-甲基-6-甲氧基-2-萘乙酸-5-苯硅基己醇酯
Figure BDA0001602245230000123
3H),7.52(dd,J＝1.2,7.6Hz,2H),7.43-7.30(m,4H),7.16-7.07(m,2H),4.20-4.09 (m,2H),4.04(t,J＝6.4Hz,2H),3.90(s,3H),3.87-3.79(m,1H),1.61-1.48(m,5H), 1.48-1.33(m,2H),1.31-1.20(m,2H),1.08-0.92(m,4H)；13C NMR(CDCl3,100 MHz):δ174.5,157.5,135.7,135.4,133.5,131.7,129.4,129.1,128.8,127.8,127.0, 126.1,125.8,118.8,105.4,64.5,55.0,45.3,32.8,28.4,24.6,18.3,16.0,15.7；HRMS (ESI)calculated for[C26H32O3SiNa]+(M+Na+)requires m/z 443.2018,found m/z 443.2019.
IV-24:(S)-(S)-5-(phenylsilyl)hexyl 2-(4-isobutylphenyl)propanoate.
2-(4-异丁基苯基)丙酸-5-苯硅基己醇酯
Figure BDA0001602245230000124
δ7.54(d,J＝6.8Hz,2H),7.43-7.32(m,3H),7.19(d,J＝8.0Hz,2H),7.08(d,J＝7.6 Hz,2H),4.23-4.13(m,2H),4.03(t,J＝6.4Hz,2H),3.67(q,J＝7.2Hz,1H),2.43(d, J＝7.2Hz,2H),1.89-1.72(m,1H),1.56-1.20(m,9H),1.14-0.98(m,4H),0.89(d,J＝ 6.8Hz,6H)；13CNMR(CDCl3,100MHz):δ174.7,140.3,137.8,135.5,131.9,129.5, 129.2,127.9,127.1,64.5,45.1,45.0,32.9,30.1,28.5,24.6,22.3,18.4,16.1,15.9； HRMS(ESI)calculatedfor[C25H36O2SiNa]+(M+Na+)requires m/z 419.2382,found m/z 419.2383.
IV-25:(2S,5S)-hexane-2,5-diylbis(phenylsilane).
(2S,5S)-2,5-二(苯硅基)己烷
Figure BDA0001602245230000131
7.43-7.31(m,6H),4.45-3.92(m,4H),1.62-1.38(m,4H), 1.16-0.99(m,8H)；13C NMR(CDCl3,100MHz):δ135.6,132.1,129.5,127.9,32.2, 16.2,16.0；HRMS(ESI)calculatedfor[C18H27Si2]+(M+H+)requires m/z 299.1651, found m/z 299.1658.
IV-26:(S)-(6-(benzyloxy)hexan-2-yl)(4-methoxyphenyl)silane.
(S)-(1-甲基-5-苄氧基戊基)-(4-甲氧基苯基)硅烷
Figure BDA0001602245230000132
(s,2H),4.44-3.90(m,2H),3.81(s,3H),3.45(t,J＝6.4Hz,2H),1.67-1.46(m,4H), 1.45-1.25(m,2H),1.16-1.01(m,4H)；13C NMR(CDCl3,100MHz):δ160.7,138.6, 137.0,128.2,127.5,127.3,122.5,113.7,72.7,70.2,54.8,33.1,29.7,25.0,16.4, 15.9；HRMS(EI)calculated for[C20H28O2Si]+requires m/z 328.1859,found m/z 328.1852.
IV-27:(S)-(6-(benzyloxy)hexan-2-yl)(4-chlorophenyl)silane.
(S)-(1-甲基-5-苄氧基戊基)-(4-氯苯基)硅烷
Figure BDA0001602245230000133
＝6.4Hz,2H),1.64-1.46(m,4H),1.46-1.30(m,2H),1.18-1.07(m,1H),1.04(d,J＝ 6.8Hz,3H)；13C NMR(CDCl3,100MHz):δ138.6,136.9,135.9,130.3,128.3,128.1, 127.5,127.4,72.8,70.2,33.1,29.7,25.1,16.2,15.9；HRMS(EI)calculated for [C19H25ClOSi]+requires m/z 332.1363,found m/z 332.1369.
IV-28:(S)-sec-butyl(4-chlorophenyl)silane
(S)-(1-甲基丙基)-(4-氯苯基)硅烷
Figure BDA0001602245230000134
(CDCl3,400MHz):δ7.49(d,J＝8.4Hz,2H),7.34(d,J＝8.0Hz,2H),4.48-3.92(m, 2H),1.60-1.48(m,1H),1.42-1.30(m,1H),1.10-1.01(m,4H),0.96(t,J＝7.6Hz, 3H)；13C NMR(CDCl3,100MHz):δ136.9,136.0,130.5,128.2,26.3,18.2,15.7, 13.2；HRMS(EI)calculated for[C10H15ClSi]+requires m/z 198.0632,found m/z 198.0635.
实施例2：产物氧化合成手性醇类化合物(应用实例)
Figure BDA0001602245230000141
参考文献：Tamao,K.In Advances in Silicon Chemistry；Larson,G.L.,Ed.；JAIPress:Greenwich,1996；Vol.3,pp 1-62.
20mL反应管中，加入IV-11(0.3056g,1.0mmol)、二氯甲烷(50mL)，0℃下搅拌并加入HBF4·Et2O(1.2497g,5.7mmol,40％Wt).搅拌3h，旋去溶剂，然后按顺序加入四氢呋喃(10mL),甲醇(10mL),氟化钾(0.2509g,4.3mmol), 碳酸氢钾(1.0025g,10mmol),H2O2(5mL,30％Wt).室温搅拌16h.加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥，旋干，PE/EtOAc＝4/1过柱得到0.1840g(0.88mmol,86％yield)目标产物。油状液体,[α]20 D＝+5.8(c 1.11, CHCl3),99.2％ee,IR(neat,cm-1):3396,3031,2926,2858,1495,1457,1372.1HNMR(CDCl3,400MHz):δ7.38-7.31(m,4H),7.31-7.26(m,1H),4.51(s,2H), 3.86-3.74(m,1H),3.48(t,J＝6.4Hz,2H),1.69-1.60(m,2H),1.54-1.33(m,5H), 1.19(d,J＝6.0Hz,3H)；13C NMR(CDCl3,100MHz):δ138.4,128.2,127.5,127.4, 72.7,70.1,67.7,38.9,29.5,23.3,22.3；HRMS(ESI)calculated for [C13H21O2]+(M+H+)requires m/z 209.1542,foundm/z 209.1526.
以下产物参照上述方法氧化成手性醇类化合物
Figure BDA0001602245230000142
Figure BDA0001602245230000151
实施例3：产物氧化合成手性硅醇类化合物(应用实例)
Figure BDA0001602245230000152
参考文献：Nakamura,M.；Matsumoto,Y.；Toyama,M.；Baba,M.；Hashimoto,Y.Chem.Pharm.Bull.2013,61,237-241.
20mL反应管中加入IV-11(0.3046g,1.0mmol),Pd/C(0.1101g,0.1mmol, 10％Wt),H2O(0.4mL)、Et2O(4.0mL)。搅拌过夜，过滤，滤液加水稀释，乙醚萃取3次，饱和食盐水洗涤，无水硫酸钠干燥。PE/EtOAc＝4/1过柱得到0.2725 g(0.82mmol,81％yield)目标产物。油状液体。[α]20 D＝-0.6(c 0.92,CHCl3),99.6％ ee,IR(cm-1):3382,3068,2925,2858,1457,1430,1366.1H NMR(CDCl3,400MHz): δ7.67-7.61(m,2H),7.46-7.26(m,8H),4.49(s,2H),3.49-3.40(m,2H),2.95-2.72(m, 2H),1.66-1.49(m,4H),1.42-1.22(m,2H),1.08-0.97(m,4H)；13C NMR(CDCl3,100 MHz):δ138.3,134.8,134.2,129.9,128.3,127.70,127.67,127.5,72.7,70.2,30.6, 29.4,24.8,19.1,13.5；HRMS(ESI)calculated for[C19H26O3SiNa]+(M+Na+)requires m/z 353.1549,found m/z 353.1561.
以下产物参照上述方法氧化成手性硅醇类化合物
Figure BDA0001602245230000161
Figure BDA0001602245230000171
Figure BDA0001602245230000181
实施例4：不同催化剂催化效率和选择性
室温下，氮气保护下，在一干燥的反应试管中加入手性FeX2-OIP络合物(0.025mmol)，烯烃(0.5mmol)，苯基硅烷(0.5mmol)，四氢呋喃(0.5mL)，叔丁醇钠(0.075mmol)，然后在室温搅拌2小时后停止反应，通过均三甲苯作内标计算1和2的核磁产率，通过高效液相色谱测1的ee值。1为手性产物，2 为非手性副产物，不同催化剂的选择性如下。
Figure BDA0001602245230000182
Entry R<sup>9</sup> R<sup>11</sup> R<sup>13</sup> R<sup>8</sup> NMR yield of 1 NMR yield of 2 Eeof 1
1 Me H Me iPr 14 48 33
2 iPr H iPr iPr 46 17 93
3 -CHPh<sub>2</sub> Me -CHPh<sub>2</sub> iPr 79 3.3 99.3
4 -CHPh<sub>2</sub> Cl -CHPh<sub>2</sub> iPr 79 6.0 99.5
5 -CHPh<sub>2</sub> -OMe -CHPh<sub>2</sub> iPr 77 2.4 99.3
6 -CHPh<sub>2</sub> -OMe -CHPh<sub>2</sub> Bn 75 6.6 98.8
7 -CHPh<sub>2</sub> -OMe -CHPh<sub>2</sub> tBu 38 17 99.4
8 -CHPh<sub>2</sub> -OMe -CHPh<sub>2</sub> Me 66 5.8 97.7
Figure BDA0001602245230000183
Figure BDA0001602245230000191
Figure BDA0001602245230000201
。

Claims (4)

1.一种手性二氢硅烷化合物的合成方法，其特征在于所述方法包括以下步骤：
以式I所示的烯烃和式II所示的硅烷为原料，手性FeX2-OIP络合物为催化剂，在还原剂存在下，反应制得式IV所示的手性二氢硅烷化合物；
Figure FDA0002731511950000011
R2SiH3 II
Figure FDA0002731511950000012
式IV中，*代表手性碳原子；
式I、式II或式IV中，R1为C1-C16的烷基，所述烷基的H不被取代或被1个以上的取代基A取代，所述取代基A包括苯基、三甲基硅基、卤素、叔丁基二甲基硅氧基、甲基磺酰氧基、对甲苯磺酰氧基、苄氧基、乙酰氧基、2-甲基-1,3-二氧-2-环戊基、邻苯二甲酰亚胺基、环己胺基、哌啶基、α-苯乙烯基、β-苯乙烯基、β-苯乙烯基甲氧基、萘基、吲哚基、吡啶基、噻吩基、呋喃基、萘基甲氧基、吡啶甲基氧基、呋喃甲基氧基、噻吩甲基氧基；2-甲基-6-甲氧基-2-萘乙酸酯基、2-(4-异丁基苯基)丙酸酯基或苯硅基；
所述R2为苯基或含有1～2个以下取代基的取代苯基：甲基、丁基、苯基、甲氧基、甲硫基、F、Cl、Br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧环戊基；
所述手性FeX2-OIP络合物催化剂如式III-1所示
Figure FDA0002731511950000013
所述还原剂为三乙基硼氢化钠、三仲丁基硼氢化钠、三乙基硼氢化锂、叔丁醇钠、叔丁醇钾、叔丁醇锂、叔戊醇钠、乙醇钠、甲醇钠、甲醇钾中的任意一种。
2.如权利要求1所述的方法，其特征在于所述R1为RA—(CH2)n—，n为1～16的整数，RA为碳链上的取代基，RA包括苯基、三甲基硅基、卤素、叔丁基二甲基硅氧基、甲基磺酰氧基、对甲苯磺酰氧基、苄氧基、乙酰氧基、2-甲基-1,3-二氧-2-环戊基、邻苯二甲酰亚胺基、环己胺基、哌啶基、α-苯乙烯基、β-苯乙烯基、β-苯乙烯基甲氧基、萘基、吲哚基、吡啶基、噻吩基、呋喃基、萘基甲氧基、吡啶甲基氧基、呋喃甲基氧基、噻吩甲基氧基；2-甲基-6-甲氧基-2-萘乙酸酯基、2-(4-异丁基苯基)丙酸酯基或苯硅基；
所述R2为苯基、对甲氧基苯基或对氯苯基。
3.如权利要求1或2所述的方法，其特征在于所述的式I所示的烯烃、式II所示的硅烷、手性FeX2-OIP络合物、还原剂的物质的量之比为1：0.1-10：0.0000005-0.05：0.0000005-0.15。
4.如权利要求1或2所述的方法，其特征在于所述方法在有机溶剂中进行，所述的有机溶剂可以为苯、四氯化碳、甲苯、四氢呋喃、乙醚、二氯甲烷、乙腈、二氧六环、石油醚、环己烷、正己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种。
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Publication number Priority date Publication date Assignee Title
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104478919A (zh) * 2014-11-18 2015-04-01 浙江大学 一种合成手性硅烷化合物的方法
CN106565764A (zh) * 2016-10-31 2017-04-19 浙江大学 一种一锅法合成α‑手性硅烷类化合物的方法
CN107235995A (zh) * 2017-06-09 2017-10-10 浙江大学 一种手性二氢硅烷化合物及其合成方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Cobalt-Catalyzed Alkyne Hydrosilylation and Sequentiao Vinylsilane Hydroboration with Markovnikov Selectivity;Ziqing Zuo et al.,;《Angew.Chem.Int.Ed.》;20160721;第55卷;第10839-10843页 *

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