CN104788274B - 一种手性1,3‑丁二烯‑2‑仲醇的制备方法 - Google Patents
一种手性1,3‑丁二烯‑2‑仲醇的制备方法 Download PDFInfo
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- 150000003333 secondary alcohols Chemical class 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
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Abstract
本发明涉及手性1,3‑丁二烯‑2‑仲醇的制备方法，其通过手性磷酸催化高联烯基硼酸酯与醛的对映选择性加成反应，制备得到手性1,3‑丁二烯‑2‑仲醇类化合物，其反应通式如下：
Description
技术领域
本发明属于有机化合物合成工艺应用技术领域，涉及手性1,3-丁二烯-2-仲醇的制备方法。
背景技术
邻位含有1,3-丁二烯结构的手性仲醇片断普遍存在于天然产物和药物中[(1)Shen,Y.-C.；Wang,L.-T.；Wang,C.-H.；Khalil,A.T.；Guh,J.-H.Chem.Pharm.Bull 2004,52,108；(2)Prakash,C.V.S.；Hoch,J.M.；Kingston,D.G.I.J.Nat.Prod.2002,65,100；(3)Iwamoto,M.；Ohtsu,H.；Tokuda,H.；Hishino,H.；Matsunaga,S.；Tanaka,R.Bioorg.Chem.Lett.2001,9,1911.]。此外，这类化合物可以通过Diels-Alder反应或Shapless环氧化反应进行衍生，是合成许多天然产物和药物的重要前驱体[(1)Yanagimoto,D.；Kawano,K.；Takahashi,K.；Ishihara,J.；Hatakeyama,S.Heterocycles,2009,77,249；(2)Xiang,A.X.；Watson,D.A.Ling,T.；Theodorakis,E.A.J.Org.Chem.1998,63,6774；(3)Hatakeyama,S.；Yoshida,M.；Esumi,T.；Iwabuchi,Y.；Irie,H.；Kawamoto,T.；Yamada,H.；Nishizawa,M.Tetrahedron Lett.1997,38,7887.]。因此，发展高效高对映选择性构建这类化合物的方法十分重要。不对称催化是合成手性化合物最为经济有效的一类方法。目前，通过不对称催化反应的方法合成手性1,3-丁二烯-2-仲醇只有以下三例报道：(1)手性BINOL-Ti催化剂催化高联烯基锡试剂与醛之间的不对称加成反应(Yu,C.-M.；Lee,S.-J.；Jeon,M.J.Chem.Soc.,Perkin Trans.1,1999,3557.)；(2)手性铬催化剂催化4-溴-2-丁炔基-三甲基硅烷试剂[(4-bromobut-2-ynyl)trimethylsilane]与醛之间的不对称加成反应(Durán-Galván,M.；Connell,B.T.Eur.J.Org.Chem.2010,2010,2445.)；(3)手性铬催化剂催化高联烯基溴试剂与醛的不对称加成反应(Naodovic,M.；Xia,G.-Y.；Yamamoto,H.Org.Lett.2008,10,4053.)。然而，以上三种方法存在底物适用范围窄、对映选择性低、产率低、采用有毒试剂或金属催化剂等诸多问题。因此，进一步开发手性1,3-丁二烯-2-仲醇类化合物的新型高效环保的合成方法具有极其重要的研究价值。
发明内容
本发明的目的在于公开一种采用手性磷酸催化剂不对称催化合成手性1,3-丁二烯-2-仲醇类化合物的方法，其操作简便，底物适用范围广，产率高，对映选择性极好(对映体过量值最高超过99％)，与已有方法相比更为绿色环保，应用性更强。
本发明解决上述技术问题所采用的技术方案是：一种手性1,3-丁二烯-2-仲醇的制备方法，其通过手性磷酸催化高联烯基硼酸酯与醛的对映选择性加成反应，制备得到手性1,3-丁二烯-2-仲醇类化合物，其反应通式如下：
式中：R为芳基或烷基。
按上述方案，采用的催化剂具有以下结构：
式中：Ar为2,4,6-三异丙基苯基。
按上述方案，采用的溶剂为甲苯、四氯化碳、甲苯与环己烷的混合溶剂或者环己烷与四氯化碳的混合溶剂。
按上述方案，反应温度为-60℃或-20℃。
按上述方案，所述的醛为苯甲醛、对甲基苯甲、对甲氧基苯甲醛、对氟苯甲醛、对氯苯甲醛、对溴苯甲醛、对甲酸甲酯基苯甲醛、对硝基苯甲醛、对三氟甲基苯甲醛、间溴苯甲醛、间甲氧基苯甲醛、邻甲基苯甲醛、1-奈甲醛、2-奈甲醛、1-蒽甲醛、2-呋喃甲醛、2-噻吩甲醛、苯丙炔醛、3-苯基丙烯醛、3-苯基-2-甲基丙烯醛、苯丙醛或环己基甲醛。
本发明的有益效果在于：通过本发明制备所得的手性1,3-丁二烯-2-仲醇类化合物，为以后手性药物和天然产物的合成奠定基础。
具体实施方式
以下实例将有助于理解本发明，但不限于本发明的内容。
实施例1
氮气氛围下，在反应瓶中加入手性磷酸(5mol％,7.6mg)，MS(30mg)，醛(0.2mmol)，甲苯(0.5mL)，冷却至-60℃，滴加高联烯基硼酸酯(0.3mmol,54mg)，反应24小时后直接进行柱分离得到目标产物。本例中，所使用的醛是苯甲醛，采用的催化剂具有以下结构：
式中：Ar为2,4,6-三异丙基苯基。
(R)-1,3-丁二烯-2-苯甲醇
黄色油状物，99％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝37.42min,tmajor＝47.19min),[α]D 20＝+99.2(c＝1.34,CHCl3).1H NMR(500MHz,CDCl3)δ7.41-7.37(m,2H),7.36-7.31(m,2H),7.30-7.26(m,1H),6.31(dd,17.8Hz,11.2Hz,1H),5.46(d,3.6Hz,1H),5.40(d,1.1Hz,1H),5.33(s,1H),5.23(d,17.8Hz,1H),5.04(d,11.2Hz,1H),2.02(d,4.0Hz,1H).13C NMR(126MHz,CDCl3)δ147.6,142.0,135.8,128.5,127.9,126.9,115.7,115.5,74.0.
实施例2
步骤同实施例1，本例中所使用的醛是对甲基苯甲醛。
(R)-1,3-丁二烯-2-对甲基苯甲醇
黄色油状物，99％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝28.29min,tmajor＝35.59min),[α]D 25＝+100.9(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.27(d,8.0Hz,2H),7.15(d,7.9Hz,2H),6.30(dd,17.8Hz,11.2Hz,1H),5.43(s,1H),5.42(s,1H),5.32(s,1H),5.20(d,17.8Hz,1H),5.03(d,11.2Hz,1H),2.33(s,3H),1.95(s,1H).13C NMR(126MHz,CDCl3)δ147.7,139.1,137.6,135.9,129.2,126.9,115,5,115.473.8,21.1.
实施例3
步骤同实施例1，本例中所使用的醛是对甲氧基苯甲醛。
(R)-1,3-丁二烯-2-对甲氧基苯甲醇
黄色油状物，98％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：AD-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tmajor＝40.30min,tminor＝47.05min),[α]D 25＝+101.3(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.30(d,8.2Hz,2H),6.87(d,8.2Hz,2H),6.30(dd,17.7Hz,11.2Hz,1H),5.43(s,1H),5.41(s,1H),5.32(s,1H),5.18(d,17.8Hz,1H),5.03(d,11.1Hz,1H),3.79(s,3H),2.00(s,1H).13C NMR(126MHz,CDCl3)δ159.3,147.7,136.0,134.2,128.3,115.3,113.9,73.5,55.3.
实施例4
步骤同实施例1，本例中所使用的醛是对氟苯甲醛。
(R)-1,3-丁二烯-2-对氟苯甲醇
黄色油状物，96％产率，>99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tmajor＝33.04min,tminor＝36.39min),[α]D 25＝+69.8(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.36(dd,8.6Hz,5.4Hz,2H),7.03(t,8.7Hz,2H),6.30(dd,17.8Hz,11.2Hz,1H),5.46(s,1H),5.40(d,0.9Hz,1H),5.34(s,1H),5.20(d,17.8Hz,1H),5.06(d,11.2Hz,1H),1.98(s,1H).19F NMR(471MHz,CDCl3)δ-114.7(s,1F).13C NMR(126MHz,CDCl3)δ162.4(d,246.5Hz),147.6,137.7(d,3.2Hz),135.7,128.6(d,8.2Hz),115.9,115.5(d,25.1Hz),115.3,73.4.
实施例5
步骤同实施例1，本例中所使用的醛是对氯苯甲醛。
(R)-1,3-丁二烯-2-对氯苯甲醇
黄色油状物，97％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝23.88min,tmajor＝25.93min),[α]D 25＝+47.6(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.37-7.27(m,4H),6.29(dd,17.8Hz,11.2Hz,1H),5.44(s,1H),5.37(s,1H),5.33(s,1H),5.21(d, 17.9Hz,1H),5.06(d,11.2Hz,1H),2.06(s,1H).13C NMR(126MHz,CDCl3)δ147.4,140.4,135.5,133.6,128.6,128.3,116.1,115.8,73.4.
实施例6
步骤同实施例1，本例中所使用的醛是对溴苯甲醛。
(R)-1,3-丁二烯-2-对溴苯甲醇
黄色油状物，96％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝24.13min,tmajor＝26.25min),[α]D 25＝+56.6(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.46(d,8.5Hz,2H),7.27(d,8.3Hz,2H),6.28(dd,17.8Hz,11.2Hz,1H),5.42(s,1H),5.36(d,1.0Hz,1H),5.33(s,1H),5.22(d,17.8Hz,1H),5.06(d,11.2Hz,1H),2.08(s,1H).13C NMR(126MHz,CDCl3)δ147.4,140.9,135.5,131.6,128.6,121.7,116.2,115.8,73.5.
实施例7
步骤同实施例1，本例中所使用的醛是对甲酸甲酯基苯甲醛。
(R)-1,3-丁二烯-2-对甲氧基甲酰基苯甲醇
黄色油状物，98％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝58.29min,tmajor＝62.13min),[α]D 25＝+29.4(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ8.00(d,8.3Hz,2H),7.47(d,8.2Hz,2H),6.29(dd,17.8Hz,11.2Hz,1H),5.52(s,1H),5.35(d,5.2Hz,2H),5.25(d,17.8Hz,1H),5.07(d,11.2Hz,1H),3.90(s,3H),2.26(s,1H).13C NMR(126MHz,CDCl3)δ166.9,147.4,147.0,135.4,129.8,129.5,126.7,116.5,115.9,73.8,52.1.
实施例8
步骤同实施例1，本例中所使用的醛是对硝基苯甲醛。
(R)-1,3-丁二烯-2-对硝基苯甲醇
黄色油状物，98％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(测试条件：OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝72.45min,tmajor＝77.45min),[α]D 25＝-7.6(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ8.20(d,8.8Hz,2H),7.59(d,8.4Hz,2H),6.29(ddd,17.8Hz,11.2Hz,0.4Hz,1H),5.58(s,1H),5.38(s,1H),5.34(d,0.8Hz,1H),5.29(d,17.8Hz,1H),5.11(d,11.2Hz,1H),2.26(s,1H).13C NMR(126MHz,CDCl3)δ149.1,147.4,147.1,135.0,127.5,123.6,117.2,116.4,73.6.
实施例9
步骤同实施例1，本例中所使用的醛是对三氟甲基苯甲醛。
(R)-1,3-丁二烯-2-对三氟甲基苯甲醇
黄色油状物；97％产率，>99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(AD-H手性柱，正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tmajor＝17.50min,tminor＝20.26min),[α]D 25＝+34.1(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.60(d,8.2Hz,2H),7.52(d,8.3Hz,2H),6.30(dd,17.8Hz,11.2Hz,1H),5.53(d,2.8Hz,1H),5.36(s,2H),5.26(d,17.8Hz,1H),5.09(dd,11.2Hz,0.5Hz,1H),2.12(d,3.8Hz,1H).19F NMR(471MHz,CDCl3)δ-62.5(s,3F).13C NMR(126MHz,CDCl3)δ146.3,144.8,134.3,128.9(q,32.5Hz),126.1,124.4(q,3.8Hz),123.1(q,272.4Hz),115.6,115.0,72.6.
实施例10
步骤同实施例1，本例中所使用的醛是间溴苯甲醛。
(R)-1,3-丁二烯-2-间溴苯甲醇
黄色油状物，99％产率，>99％对映体过量值,对映体过量值通过高效液相色谱的方法 测定(OD-H手性柱,正己烷/异丙醇＝99/1,流速＝0.6mL/min,波长＝254nm,tminor＝43.67min,tmajor＝59.78min),[α]D 25＝+46.4(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.55(t,1.6Hz,1H),7.42-7.40(m,1H),7.31(d,7.7Hz,1H),7.21(t,7.8Hz,1H),6.29(dd,17.8Hz,11.2Hz,1H),5.43(d,2.5Hz,1H),5.38-5.32(m,2H),5.24(d,17.8Hz,1H),5.08(d,11.2Hz,1H),2.09(d,3.4Hz,1H).13C NMR(126MHz,CDCl3)δ146.2,143.2,134.4,129.8,129.0,128.9,124.5,121.6,115.4,114.8,72.5.
实施例11
步骤同实施例1，本例中所使用的醛是间甲氧基苯甲醛。
(R)-1,3-丁二烯-2-间甲氧基苯甲醇
黄色油状物，99％产率，>99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(AD-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tmajor＝45.33min,tminor＝53.77min),[α]D 25＝+64.9(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.25(t,7.9Hz,1H),7.02-6.92(m,2H),6.82(dd,8.2Hz,2.0Hz,1H),6.30(dd,17.8Hz,11.2Hz,1H),5.43(s,1H),5.39(s,1H),5.32(s,1H),5.25(d,17.8Hz,1H),5.05(d,11.2Hz,1H),3.79(s,4H),2.06(s,1H).13C NMR(126MHz,CDCl3)δ159.8,147.5,143.7,135.8,129.5,119.3,115.8,115.5,113.3,112.4,74.0,55.2.
实施例12
步骤同实施例1，本例中所使用的醛是邻甲基苯甲醛。
(R)-1,3-丁二烯-2-邻甲基苯甲醇
黄色油状物，99％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝15.43min,tmajor＝19.64min),[α]D 25＝+91.1(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.43-7.35(m,1H),7.18-7.15(m,3H),6.38(dd,17.8Hz,11.1Hz,1H),5.65(s,1H),5.34(s,1H),5.23(s,1H), 5.19(d,17.8Hz,1H),5.07(d,11.1Hz,1H),2.36(s,3H),1.87(s,1H).13C NMR(126MHz,CDCl3)δ147.3,139.8,136.4,135.9,130.5,127.8,126.2,126.3,116.5,115.0,70.2,19.0.
实施例13
步骤同实施例1，本例中所使用的醛是1-奈甲醛。
(R)-1,3-丁二烯-2-(1-萘甲醇)
黄色油状物，98％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝45.47min,tmajor＝103.00min),[α]D 25＝+42.9(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ8.10(d,8.3Hz,1H),7.90-7.84(m,1H),7.80(d,8.2Hz,1H),7.60(d,7.1Hz,1H),7.54-7.44(m,3H),6.44(dd,17.8Hz,11.1Hz,1H),6.24(d,2.4Hz,1H),5.40(s,1H),5.32(d,1.0Hz,1H),5.22(d,17.8Hz,1H),5.07(d,11.1Hz,1H),2.08(s,1H).13C NMR(126MHz,CDCl3)δ147.4,137.3,136.5,133.9,131.1,128.8,128.6,126.3,125.7,125.4,124.5,123.5,117.2,115.1,69.8.
实施例14
步骤同实施例1，本例中所使用的醛是2-奈甲醛。
(R)-1,3-丁二烯-2-(2-萘甲醇)
黄色油状物，99％产率，>99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝65.72min,tmajor＝70.90min),[α]D 25＝+77.3(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.86(s,1H),7.84-7.81(m,8.8Hz,6.2Hz,3H),7.51-7.43(m,3H),6.34(dd,17.8Hz,11.2Hz,1H),5.63(s,1H),5.45(d,1.0Hz,1H),5.38(s,1H),5.28(d,17.8Hz,1H),5.04(d,11.2Hz,1H),2.13(s,1H).13C NMR(126MHz,CDCl3)δ146.5,138.4,134.8,132.3,132.0,127.3,127.1,126.7,125.1,125.0,124.7,123.8,115.0,114.6,73.2.
实施例15
步骤同实施例1，本例中所使用的醛是1-蒽甲醛。
(R)-1,3-丁二烯-2-(9-蒽甲醇)
黄色油状物，96％产率，97％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tmajor＝47.72min,tminor＝53.60min),[α]D 25＝+30.1(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ8.51(d,8.1Hz,2H),8.43(s,1H),7.99(dd,7.0Hz,2.5Hz,2H),7.48-7.45(m,4H),6.91(s,1H),6.34(dd,17.7Hz,11.2Hz,1H),5.45-5.37(m,2H),5.23(s,1H),5.01(d,11.1Hz,1H),2.42(d,3.0Hz,1H).13C NMR(126MHz,CDCl3)δ146.5,135.2,131.2,130.6,129.1,128.2,127.6,124.8,123.9,123.8,114.6,114.3,69.0.
实施例16
步骤同实施例1，本例中所使用的醛是2-呋喃甲醛。
(R)-1,3-丁二烯-2-(2-呋喃甲醇)
黄色油状物，95％产率，97％对映体过量值,对映体过量值通过高效液相色谱的方法测定(AD-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tminor＝23.52min,tmajor＝24.92min),[α]D 25＝+53.0(c＝0.2,CHCl3).1H NMR(500MHz,CDCl3)δ7.42-7.36(m,1H),6.38(dd,17.9Hz,11.2Hz,1H),6.33(dd,3.2Hz,1.8Hz,1H),6.26(d,3.2Hz,1H),5.52(d,4.3Hz,1H),5.46(d,1.0Hz,1H),5.36(s,1H),5.25(d,17.8Hz,1H),5.09(d,11.2Hz,1H),2.07(d,4.8Hz,1H).13C NMR(126MHz,CDCl3)δ155.0,145.4,142.4,135.7,116.2,115.1,110.4,107.6,67.5.
实施例17
步骤同实施例1，所使用的溶剂为：甲苯:环己烷＝1:1，本例中所使用的醛是2-噻吩甲醛。
(R)-1,3-丁二烯-2-(2-噻吩甲醇)
黄色油状物，98％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝36.16min,tmajor＝43.88min),[α]D 25＝+70.5(c＝0.8,CHCl3).1H NMR(500MHz,CDCl3)δ7.27-7.25(m,1H),7.01(d,3.5Hz,1H),6.96(dd,5.0Hz,3.5Hz,1H),6.36(dd,17.8Hz,11.2Hz,1H),5.71(d,3.9Hz,1H),5.50(d,1.0Hz,1H),5.34(s,1H),5.28(d,17.8Hz,1H),5.10(d,11.2Hz,1H),2.12(d,4.3Hz,1H).13C NMR(126MHz,CDCl3)δ147.4,146.3,135.5,126.8,125.4,125.3,115.5,69.6.
实施例18
步骤同实施例1，本例中所使用的醛是苯丙炔醛。
(R)-1,3-丁二烯-2-(苯乙炔甲醇)
黄色油状物，98％产率，99％对映体过量值,对映体过量值通过高效液相色谱的方法测定(AS-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tmajor＝15.02min,tminor＝18.61min),[α]D 25＝-11.0(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.49-7.39(m,2H),7.35-7.27(m,3H),6.43(dd,17.8Hz,11.2Hz,1H),5.63-5.56(m,2H),5.35(s,1H),5.29(s,1H),5.25(d,11.2Hz,1H),2.17(s,1H).13C NMR(126MHz,CDCl3)δ145.0,134.9,131.7,128.6,128.3,122.5,116.6,115.8,88.0,86.3,63.1.
实施例19
步骤同实施例1，本例中所使用的醛是3-苯基丙烯醛。
(S,E)-1,3-丁二烯-2-(苯乙烯甲醇)
黄色油状物，98％产率，98％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷/异丙醇＝96/4,流速＝0.6mL/min,波长＝254nm,tminor＝31.12min,tmajor＝34.43min),[α]D 25＝+16.7(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.39(dd,8.1Hz, 0.9Hz,2H),7.31(t,7.6Hz,2H),7.25-7.23(m,1H),6.68(d,15.9Hz,1H),6.38(dd,17.8Hz,11.2Hz,1H),6.30(dd,15.9Hz,6.2Hz,1H),5.44(d,17.8Hz,1H),5.37(d,1.0Hz,1H),5.25(s,1H),5.15(d,11.2Hz,1H),5.08(d,5.9Hz,1H),1.88(s,1H).13C NMR(126MHz,CDCl3)δ147.4,136.6,135.9,131.3,130.3,128.6,127.8,126.6,115.3,115.2,72.3.
实施例20
步骤同实施例1，本例中所使用的醛是3-苯基-2-甲基丙烯醛。
(S,E)-1,3-丁二烯-2-((2-甲基)苯乙烯甲醇)
黄色油状物，95％产率，96％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OD-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tminor＝34.54min,tmajor＝38.48min),[α]D 25＝+42.3(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.36-7.31(m,2H),7.29(t,4.1Hz,2H),7.24-7.19(m,1H),6.68(s,1H),6.35(dd,17.8Hz,11.2Hz,1H),5.45(dd,17.7Hz,0.4Hz,1H),5.38(d,1.1Hz,1H),5.32(s,1H),5.10(d,11.2Hz,1H),4.93(s,1H),1.83(s,1H),1.80(d,1.3Hz,3H).13C NMR(126MHz,CDCl3)δ145.1,137.2,136.5,134.9,127.9,127.1,126.3,125.6,114.6,114.0,76.2,12.9.
实施例21
步骤同实施例1，本例中所用的溶剂为：环己烷:四氯化碳＝1:1，反应温度为-20℃，本例中所使用的醛是苯丙醛。
(S)-1,3-丁二烯-2-苯丙醇
黄色油状物，96％产率，92％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OD-H手性柱,正己烷/异丙醇＝99/1,流速＝1.0mL/min,波长＝254nm,tmajor＝39.98min,tminor＝46.51min),[α]D 25＝-41.0(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ7.30-7.27(m,2H),7.23-7.16(m,3H),6.33(dd,17.8Hz,11.2Hz,1H),5.27(d,1.0Hz,1H),5.22(d,17.8Hz,1H),5.17(s,1H),5.07(d,11.2Hz,1H),4.45-4.41(m,1H),2.82-2.77(m,1H),2.74-2.68(m,1H),2.07-1.95(m,1H),1.95-1.83(m,1H),1.57(d,3.7Hz,1H).13C NMR(126MHz,CDCl3)δ149.1, 141.9,136.1,128.5,128.4,125.9,114.4,114.1,70.7,37.9,32.0.
实施例22
步骤同实施例1，本例中所使用的溶剂为四氯化碳，反应温度为-20℃，本例中所使用的醛是环己基甲醛。
(S)-1,3-丁二烯-2-环己基甲醇
黄色油状物，92％产率，90％对映体过量值,对映体过量值通过高效液相色谱的方法测定(OJ-H手性柱,正己烷,流速＝1.0mL/min,波长＝254nm,tmajor＝12.08min,tminor＝13.49min),[α]D 25＝+5.3(c＝1.0,CHCl3).1H NMR(500MHz,CDCl3)δ6.33(dd,17.7Hz,11.1Hz,1H),5.38(d,17.7Hz,1H),5.20(s,1H),5.13(s,1H),5.10(d,11.2Hz,1H),4.12(d,6.0Hz,1H),1.87(d,12.4Hz,1H),1.81-1.47(m,6H),1.30-0.94(m,5H).13C NMR(126MHz,CDCl3)δ147.0,135.2,113.7,113.6,75.9,40.9,29.0,26.7,25.5,25.3,25.1。
Claims (1)
1.一种手性1,3-丁二烯-2-仲醇的制备方法，其通过手性磷酸催化高联烯基硼酸酯与醛的对映选择性加成反应，反应温度为-60℃或-20℃，采用的溶剂为甲苯、四氯化碳、甲苯与环己烷的混合溶剂或者环己烷与四氯化碳的混合溶剂，制备得到手性1,3-丁二烯-2-仲醇类化合物，其反应通式如下：
所述的醛为苯甲醛、对甲基苯甲醛、对甲氧基苯甲醛、对氟苯甲醛、对氯苯甲醛、对溴苯甲醛、对甲酸甲酯基苯甲醛、对硝基苯甲醛、对三氟甲基苯甲醛、间溴苯甲醛、间甲氧基苯甲醛、邻甲基苯甲醛、1-萘甲醛、2-萘甲醛、1-蒽甲醛或环己基甲醛；式中：R为上述醛的对应基团；
采用的催化剂具有以下结构：
式中：Ar为2,4,6-三异丙基苯基。
Priority Applications (1)
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