CN106748917B - 一种手性亚磺酰胺配体及其制备方法和应用 - Google Patents

一种手性亚磺酰胺配体及其制备方法和应用 Download PDF

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CN106748917B
CN106748917B CN201611121712.4A CN201611121712A CN106748917B CN 106748917 B CN106748917 B CN 106748917B CN 201611121712 A CN201611121712 A CN 201611121712A CN 106748917 B CN106748917 B CN 106748917B
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sulfenamide
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赵晓明
赵明珠
田亚伟
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Abstract

本发明涉及一种新型手性亚磺酰胺配体的制备方法及其在金属钯催化的不对称烯丙基化反应中的应用。在干燥的四氢呋喃中，控制反应温度为25℃～50℃，以水杨酸或其类似物为原料与羰基二咪唑反应制得活性中间体。在干燥的四氢呋喃，室温下手性叔丁基亚磺酰胺与氢化钾反应，随后加入水杨酸或其类似物的活性中间体，继续反应得到手性亚磺酰胺配体。与现有技术相比，该制备方法步骤简洁高效，配体结构骨架为独立原创。进一步将所述新型手性亚磺酰胺配体应用在金属钯催化的不对称烯丙基化反应中，在最优化条件下，能取得良好催化效果。

Description

一种手性亚磺酰胺配体及其制备方法和应用
技术领域
本发明涉及一种新型手性亚磺酰胺配体化合物及其制备方法，进一步涉及其在金属钯催化的不对称烯丙基化反应中的应用。
背景技术
在金属催化的不对称反应领域，手性配体的合成一直是最重要的热点和难点。目前熟知的配体主要集中在手性含磷配体、手性含氮配体，手性含硫配体和手性含氧配体。手性硫配体则集中在手性亚砜配体及手性亚磺酰胺配体中。文献报道的手性亚磺酰胺配体具有优异的催化效果。(a)Trost,B.M.；Rao,M. Angew.Chem.Int.Ed.2015,54,5026-5043.(b)Jin,S.S.；Wang,H.；Xu,M.H. Chem.Commun.2011,47,7230-7232.(c)Feng,X.Q.；Wang,Y.Z.；Wei,B.B.； Yang,J.；Du,H.F.Org.Lett.2011,13,3300-3303.(d)Zhu,T.S.；Jin,S.S.；Xu, M.H.Angew.Chem.Int.Ed.2012,51,780-783.(e)Wang,H.；Zhu,T.S.；Xu,M.H.J.Am.Chem.Soc.2013,135,971-974.(f)Feng,X.Q.；Wang,Y.Z.；Wei,B.B.； Yang,J.；Du,H.F.Org.Lett.2011,13,3300-3303.(g)Liu,Z.Q.；Feng,X.Q.； Du,H.F.Org.Lett.2012,14,3154-3157.(h)Chen,Q.；Chen,C.；Guo,F.；Xia,W. Chem.Commun.2013,49,6433-6435.(i)Zhang,Z.；Chen,P.；Li,W.；Niu,Y.； Zhao,X.；Zhang,J.Angew.Chem.Int.Ed.2014,53,4350-4354.13-21.但是文献中所报道配体基本制备方法复杂。同时该类配体基本都应用于不对称加成反应中，其应用具有局限性，其中用于金属钯催化的不对称烯丙基化虽然已有研究，但文献报道较少。(a)Gao,N.；Zhao,X.M.；Cai,C.S.；Cai,J.W.Org.Biomol.Chem.2015,13,9551-9558.(b)Zhang,M.；Zhao,M.；Zheng,P.；Zhang,H.；Zhao,X.J.Fluorine Chem.2016,189,13-21。
发明内容
本发明的目的就是为了提供一种新型的手性亚磺酰胺配体的制备方法及其在不对称催化反应领域中的应用。
本发明的目的可以通过以下技术方案来实现：
一种新型手性亚磺酰胺配体，该化合物的分子式如下：
其中*为手性原子，R选自氢、甲氧基、并环的苯基。
一种新型手性亚磺酰胺配体化合物的制备方法，包括以下步骤：
氩气保护下，在反应管中加入原料水杨酸或其类似物和干燥的四氢呋喃，分批加入碳酰二咪唑，反应释放出CO2，室温搅拌0.5小时后升温至50℃继续搅拌 1小时后结束反应，将反应液冷却至室温，浓缩得活性中间体，直接用于下一步反应。在制备活性中间体同时，另备干燥的反应管，加入手性叔丁基亚磺酰胺和干燥的四氢呋喃，加入氢化钾，室温下搅拌0.5小时后加入活性中间体，继续搅拌2 小时后，加入1M HCl淬灭反应至弱酸性，乙酸乙酯萃取，饱和食盐水洗涤，无水硫酸钠干燥，过滤，滤液旋干得粗品，硅胶柱层析纯化制备得手性亚磺酰胺配体类化合物。
其反应方程式如下：
其中CDI为碳酰二咪唑，THF为四氢呋喃，rt为室温，KH为分散于矿物油中30％的氢化钾悬浮液。
所述的水杨酸或其类似物、碳酰二咪唑、叔丁基亚磺酰胺、KH的摩尔比为1:1:1:2。
所述的水杨酸或其类似物的结构式选自但不限于：
所述的手性叔丁基亚磺酰胺化合物结构式为：
所述的碳酰二咪唑化合物结构式为：
采用本发明方法所得产物手性亚磺酰胺配体类化合物可以经过薄层层析或柱层析的方法来分离。如用薄层层析、柱层析的方法，所用展开剂为非极性溶剂与极性溶剂的混合溶剂。推荐溶剂可为石油醚-二氯甲烷，石油醚-乙酸乙酯，石油醚-乙醚等混合溶剂，其体积比可以分别为：非极性溶剂/极性溶剂＝ 1/2。例如：石油醚/乙酸乙酯＝1/2,石油醚/二氯甲烷＝1/2。
本发明提供了一种新型的制备新型手性亚砜配体的方法。进一步将该配体应用于金属钯催化的不对称烯丙基化反应中，有良好的催化活性。一种新型手性亚磺酰胺配体化合物的应用，其反应步骤如下：
在有机溶剂中，控制反应温度为0℃～25℃，以对称烯丙基醋酸酯化合物和2-氟乙酰乙酸乙酯为原料，以[Pd(C3H5)Cl]2与手性亚磺酰胺配体作用生成的络合物作为催化剂，在添加剂的作用下反应12～24小时制得(E)-3,5-二芳基-2- 乙酰基-2-氟-4-戊烯酸乙酯类化合物。
反应方程式如下：
其中L为上文所述制备的新型手性亚磺酰胺配体，Add.为添加剂，Sol.为有机溶剂，T为反应温度，*为手性碳原子。
所述的对称烯丙基醋酸酯的结构式为：其中R1选自芳基。
所述的2-氟乙酰乙酸乙酯的结构式为：
所述的(E)-3,5-二芳基-2-乙酰基-2-氟-4-戊烯酸乙酯类化合物的结构式为：其中R1选自芳基。
所述的添加剂选自磷酸钾、磷酸钠、叔丁醇钾、碳酸钾、碳酸铯、氟化铯，优选磷酸钾。
所述的有机溶剂选自四氢呋喃、二氯甲烷、1,4-二氧六环、甲苯或四氢呋喃与1,4-二氧六环的混合溶剂，优选四氢呋喃与1,4-二氧六环的混合溶剂。
所述的反应温度选自0℃～25℃，优选25℃。
所述的对称烯丙基醋酸酯化合物、2-氟乙酰乙酸乙酯、[Pd(C3H5)Cl]2、手性亚磺酰胺配体、添加剂的摩尔比为1:3:0.04:0.08:3。
采用本发明方法所得产物(E)-3,5-二芳基-2-乙酰基-2-氟-4-戊烯酸乙酯类化合物可以经过硅胶薄层层析或柱层析方法来分离。如用硅胶薄层层析、柱层析的方法，所用展开剂为非极性溶剂与极性溶剂的混合溶剂。推荐溶剂可为石油醚-二氯甲烷，石油醚-乙酸乙酯，石油醚-乙醚等混合溶剂，其体积比可以分别为：非极性溶剂/极性溶剂＝20-10/1。例如：石油醚/乙酸乙酯＝20-10/1,石油醚/二氯甲烷＝20-10/1。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
实施例1～4
一种手性亚磺酰胺配体类化合物的合成
所述实施例1～4反应方程式为：
所述实施例1～4具体制备方法如下：
氩气保护下，在10mL反应管中加入原料1(1.0mmol)和5mL干燥的四氢呋喃，分批加入碳酰二咪唑(CDI，1.0mmol)，反应释放出CO2，室温搅拌0.5小时后升温至50℃继续搅拌1小时后结束反应，将反应液冷却至室温，浓缩得活性中间体2，直接用于下一步反应。在制备活性中间体同时，另备10mL干燥的反应管，加入R-叔丁基亚磺酰胺(1.0mmol)和5mL干燥的四氢呋喃，加入KH(2.0mmol，30％in oil)，室温下搅拌0.5小时后加入活性中间体2，继续搅拌2小时后，加入1M HCl淬灭反应至弱酸性，乙酸乙酯萃取，饱和食盐水洗涤，无水硫酸钠干燥，过滤，滤液旋干得粗品，硅胶柱层析(石油醚/乙酸乙酯＝1/2，v/v)纯化，得目标产物手性亚磺酰胺配体类化合物L。
所述实施例1～4，当R不同时目标产物L的结构及性质分别如下：
其中：实施例1
目标产物L1:N-叔丁基亚磺酰基-2-羟基苯甲酰胺
白色固体，熔点144.6–145.9℃，62％收率，
1H NMR(400MHz,CDCl3):δ7.78(d,J＝7.8Hz,1H),7.39(t,J＝7.4Hz,1H), 7.01(d,J＝8.1Hz,1H),6.88(t,J＝7.5Hz,1H),1.36(s,9H).13C NMR(101MHz, CDCl3):δ168.94,159.16,135.22,129.55,119.79,118.01,115.40,57.05,22.26.IR (KBr):νmax(cm-1)＝3259,2963,2930,2854,1677,1605,1464,1408,1393,1304,1232, 1107,1032.HRMS(ESI-TOF)m/z calcd.for C11H16NO3S+[M+H]+:242.0845；found: 242.0841.
实施例2
目标产物L2:N-叔丁基亚磺酰基-3-羟基-2-萘甲酰胺
黄色固体，熔点168.1–170.9℃，60％收率，
1H NMR(400MHz,CDCl3):δ8.26(s,1H),7.66(d,J＝8.2Hz,1H),7.59(d, J＝8.1Hz,1H),7.48(t,J＝7.4Hz,1H),7.31(s,1H),7.28(t,J＝7.4Hz,1H), 1.44(s,9H).13C NMR(101MHz,CDCl3):δ167.63,152.83,137.06,133.05, 129.15,128.94,127.47,126.02,124.11,117.86,111.93,56.86,22.33.IR(KBr): νmax(cm-1)＝3291,3150,2967,1622,1596,1474,1454,1418,1395,1365,1205, 1179,1097.HRMS(ESI-TOF)m/z calcd.forC15H17NNaO3S+[M+Na]+: 314.0821；found:314.0813.
实施例3
目标产物L3:N-叔丁基亚磺酰基-1-羟基-2-萘甲酰胺
黄色固体，熔点197.8–198.9℃，55％收率，
1H NMR(400MHz,CDCl3):δ8.40(d,J＝8.3Hz,1H),7.78(d,J＝8.0Hz, 1H),7.64(t,J＝7.4Hz,1H),7.55(t,J＝8.7Hz,2H),7.33(d,J＝8.8Hz,1H), 1.44(s,9H).13C NMR(101MHz,CDCl3):δ171.77,162.05,136.99,129.80, 127.45,126.13,125.31,124.11,121.48,118.84,105.47,58.07,22.26.IR(KBr): νmax(cm-1)＝3068,2972,2866,1618,1595,1475,1455,1410,1391,1318,1277, 1251,1061.HRMS(ESI-TOF)m/z calcd.forC15H17NNaO3S+[M+Na]+: 314.0821；found:314.0797.
实施例4
目标产物L4:N-叔丁基亚磺酰基-1-羟基-3-甲氧基苯甲酰胺
无色油状物，52％收率，
1H NMR(400MHz,CDCl3):δ7.74(d,J＝7.4Hz,1H),6.46(s,1H),6.35(d, J＝7.7Hz,1H),3.77(s,3H),1.26(s,9H).13C NMR(101MHz,CDCl3):δ 170.97,164.92,162.71,131.00,109.49,106.84,101.57,55.96,55.39,22.38.IR (KBr):νmax(cm-1)＝3460,2961,2926,2854,1646,1610,1440,1245,1220,1169, 1071,1032.HRMS(ESI-TOF)m/z calcd.forC12H18NO4S+[M+H]+:272.0951； found:272.0929.
所述原料1选自其羟基用甲基或烯丙基保护的化合物，可得目标产物手性亚磺酰胺配体类化合物的进一步形式。下面结合具体实施例对本发明进行详细说明。
实施例5:N-叔丁基亚磺酰基-2-甲氧基苯甲酰胺的制备，其制备过程与所述实施例1～4相似。
白色固体，熔点58.5–60.6℃，92％收率，
1H NMR(400MHz,CDCl3):δ9.47(br,1H),8.22(d,J＝7.0Hz,1H), 7.57–7.50(m,1H),7.13(t,J＝7.7Hz,1H),7.03(d,J＝8.4Hz,1H),4.02(s,3H), 1.35(s,9H).13C NMR(101MHz,CDCl3):δ165.50,157.78,134.70,132.77, 121.75,119.52,111.75,56.62,56.41,22.29.IR(KBr):νmax(cm-1)＝3172,2985, 2956,2838,1680,1599,1470,1440,1421,1292,1250,1230,1070,1045. HRMS(ESI-TOF)m/z calcd.for C12H18NO3S+[M+H]+:256.1002；found: 256.0988.
实施例6:N-叔丁基亚磺酰基-2-烯丙基氧基苯甲酰胺的制备，其制备过程与所述实施例1～4相似。
白色固体，熔点65.8–67.6℃，92％收率，
1H NMR(400MHz,CDCl3):δ8.22(dd,J＝7.8,1.2Hz,1H),7.55–7.49(m, 1H),7.12(t,J＝7.6Hz,1H),7.01(d,J＝8.3Hz,1H),6.12(ddd,J＝16.5,11.7, 6.0Hz,1H),5.50(d,J＝17.2Hz,0H),5.43(d,J＝9.8Hz,0H),4.73(d,J＝5.9 Hz,2H),1.33(s,9H).13C NMR(101MHz,CDCl3):δ165.52,156.95,134.50, 133.04,131.46,121.92,120.88,112.80,70.54,56.50,22.36.IR(KBr):νmax (cm-1)＝3131,2954,2871,1672,1600,1471,1456,1427,1294,1241,1127,1073, 1000.HRMS(ESI-TOF)m/z calcd.for C14H20NO3S+[M+H]+:282.1158；found: 282.1152.
实施例7～23
由实施例1～6制备的新型亚磺酰胺配体，进一步将该配体应用于金属钯催化的对称烯丙基醋酸酯与2-氟乙酰乙酸乙酯的不对称烯丙基化反应。在不同新型磺酰胺配体、不同添加剂、不同溶剂及反应温度的情况下，考察反应产物及产率。
所述实施例7～23反应方程式如下：
其中L为所述实施例1～6制备的新型手性亚磺酰胺配体，Add.为添加剂， Sol.为溶剂，rt为室温，*为手性碳原子。
所述实施例7～23具体制备方法如下：
在一干燥的氩气保护的反应管内，依次加入[Pd(C3H5)Cl]2(0.004mmol)、亚磺酰胺配体L(0.008mmol)和2.0mL有机溶剂，室温下反应30分钟。加入化合物3(0.1mmol)，室温搅拌10分钟后，加入2-氟代乙酰乙酸乙酯4(0.3mmol) 和添加剂(0.3mmol)，于室温下反应12小时。反应结束后，硅藻土过滤，浓缩，残留物硅胶柱层析(石油醚/乙酸乙酯＝20/1，v/v)纯化，得到目标化合物5。
所述实施例7～23的结果如下表所示：
其中配体L1～L6为所述实施例1～6制备的新型手性亚磺酰胺配体；THF 为四氢呋喃、Dioxane为二氧六环、DCM为二氯甲烷、Toluene为甲苯、 THF/Dioxane为四氢呋喃与二氧六环的混合溶剂(1/1，v/v)；N.R.指反应未能进行；trace指反应产物为痕量；a产物的分离收率；bdr为非对映选择性；cee 为对映选择性；d反应温度为0℃。
所述实施例12的目标化合物5获得了98％的分离收率、1.6:1的dr值、80％与79％的ee值。该实施例的条件为优选：优选配体L1、添加剂为K3PO4、反应溶剂为THF/Dioxane为混合溶剂(1/1，v/v)，室温反应时间12小时。
实施例24～33：
在所述实施例12优选条件下对对称烯丙基醋酸酯底物进行了拓展，来进行实施例24～33的操作。
所述实施例24～33反应方程式如下：
其中R1选自芳基、优选苯基、取代苯基、萘基，L1为所述实施例1制备的新型手性亚磺酰胺配体，K3PO4为添加剂磷酸钾，THF/Dioxane为四氢呋喃与二氧六环的混合溶剂(1/1，v/v)，rt为室温，*为手性碳原子。
所述实施例24～32具体制备方法如下：
在一干燥的氩气保护的反应管内，依次加入[Pd(C3H5)Cl]2(0.004mmol)、手性亚磺酰胺配体L1(0.008mmol)和2.0mL混合溶剂THF/Dioxane(1/1，v/v)，室温下反应30分钟。加入化合物6(0.1mmol)，室温搅拌10分钟后，加入2-氟代乙酰乙酸乙酯4(0.3mmol)和添加剂磷酸钾(0.3mmol)，于室温下反应12～24 小时。反应结束后，硅藻土过滤，浓缩，残留物硅胶柱层析(石油醚/乙酸乙酯＝ 20-10/1，v/v)纯化，得到目标化合物7。
所述实施例24～32，当R1不同时目标产物7的结构及性质分别如下：
实施例24
目标产物7：(E)-3,5-二(3-氯苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
无色油状物，98％收率，dr＝1.6:1，80％和79％ee[手性柱Daicel CHIRALCEL OJ-H(0.46cm×25cm)；正己烷/异丙醇＝98/2；流速＝1.0 mL/min；检测波长＝214nm；保留时间tR(major)＝16.984min,19.423min； tR(minor)＝21.968min,25.166min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.42–7.17(m,13H), 6.61–6.21(m,3.3H),4.52(dd,J＝32.6,8.8Hz,1.6H),4.37–4.16(m,2H),4.06(m, 1.3H),2.32(d,J＝5.7Hz,1.9H),2.01(d,J＝5.6Hz,3H),1.27(t,J＝7.1Hz,3H), 1.06(t,J＝7.1Hz,1.9H).13C NMR(101MHz,CDCl3,stereoisomeric mixture): δ201.32(d,J＝29.8Hz),201.14(d,J＝29.9Hz),164.66(d,J＝25.7Hz),164.26 (d,J＝25.9Hz),139.01,138.42,138.10,138.03,134.60,134.46,133.61,133.30, 130.04,130.02,129.85,129.52(d,J＝2.5Hz),129.19(d,J＝2.6),128.11,128.06, 128.05,128.00,127.70(d,J＝2.2Hz),127.12(d,J＝2.6Hz),126.38,126.33, 125.79,125.75,125.60,125.55,124.89,124.80,102.68(d,J＝206.1Hz),102.52 (d,J＝207.9Hz),63.09,62.84,52.88(d,J＝18.1Hz),52.82(d,J＝18.2Hz), 26.85,26.84,14.18,13.77.19F NMR(376MHz,CDCl3,stereoisomeric mixture): δ-174.49,-175.05.IR(KBr):νmax(cm-1)＝3064,2982,2932,2854,1754,1734, 1594,1570,1476,1431,1356,1246,1205,967,913,781,742.HRMS(ESI-TOF) m/z calcd.for C21H19Cl2FNaO3 +[M+Na]+:431.0587；found:431.0592.
实施例25
目标产物7：(E)-3,5-二(3-氟苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
无色油状物，85％收率，dr＝1.5:1，77％和70％ee[手性柱Daicel CHIRALCEL IF3+IG(0.46cm×25cm)；正己烷/异丙醇＝96/4；流速＝0.7 mL/min；检测波长＝214nm；保留时间tR(major)＝26.370min,32.750min；tR (minor)＝22.317min,31.817min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.34–6.84(m,13.3H), 6.64–6.26(m,5H),4.55(dd,J＝32.6,9.0Hz,1.7H),4.27(qd,J＝7.1,3.6Hz,2H), 4.06(qd,J＝7.1,3.0Hz,1H),2.33(d,J＝5.7Hz,2H),2.00(d,J＝5.6Hz,3H), 1.27(t,J＝7.1Hz,3H),1.05(t,J＝7.1Hz,2H).13C NMR(101MHz,CDCl3, stereoisomeric mixture):δ201.39(d,J＝29.8Hz),201.21(d,J＝29.8Hz),164.70 (d,J＝25.7Hz),164.30(d,J＝26.0Hz),163.03(dd,J＝245.7,1.1Hz),162.75(d, J＝246.5Hz),139.45(d,J＝7.2Hz),138.81(d,J＝7.1Hz),138.61(d,J＝7.5 Hz),138.53(d,J＝7.5Hz),133.73(d,J＝2.5Hz),133.46(d,J＝2.4Hz),130.29 (d,J＝8.0Hz),130.22(d,J＝8.2Hz),130.09(d,J＝8.4Hz),125.69(d,J＝3.9 Hz),125.55(d,J＝5.0Hz),125.25(dd,J＝2.4,2.4Hz),124.69(dd,J＝2.6,2.6 Hz),122.50(d,J＝2.7Hz),122.43(d,J＝2.7Hz),116.42(dd,J＝22.1,2.6Hz), 116.02(dd,J＝22.1,2.9Hz),114.90(d,J＝21.4Hz),114.88(d,J＝21.4Hz), 114.86(d,J＝21.2Hz),114.75(d,J＝21.0Hz),112.98(d,J＝21.9Hz),112.95 (d,J＝21.8Hz),102.73(d,J＝206.0Hz),102.58(d,J＝207.8Hz),63.06,62.78, 52.90(dd,J＝18.1,1.4Hz),52.86(dd,J＝18.0,1.4Hz),26.82,14.16,13.75. 19F NMR(376MHz,CDCl3,stereoisomeric mixture):δ-112.03,-112.28,-113.26, -113.27,-174.56,-175.13.IR(KBr):νmax(cm-1)＝3070,3039,2984,2939,1755, 1735,1612,1585,1489,1448,1358,1253,1200,1147,1016,969,913,783,741. HRMS(ESI-TOF)m/z calcd.for C21H19F3NaO3 +[M+Na]+:399.1179；found:399.1182.
实施例26
目标产物7：(E)-3,5-二(3-溴苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
无色油状物，94％收率，dr＝1.8:1，90％和94％ee[手性柱Daicel CHIRALCEL OJ-H(0.46cm×25cm)；正己烷/异丙醇＝98/2；流速＝1.0 mL/min；检测波长＝214nm；保留时间tR(major)＝18.885min,21.419min；tR (minor)＝24.138min,28.520min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.55–7.11(m,12.5H), 6.52–6.26(m,3.2H),4.51(dd,J＝32.6,8.7Hz,1.6H),4.27(qd,J＝7.1,4.6Hz, 2H),4.06(qd,J＝7.1,3.6Hz,1.1H),2.32(d,J＝5.7Hz,1.7H),2.02(t,J＝8.6Hz, 3H),1.27(t,J＝7.1Hz,3H),1.06(t,J＝7.1Hz,1.7H).13C NMR(101MHz, CDCl3,stereoisomeric mixture):δ201.30(d,J＝29.8Hz),201.11(d,J＝29.8Hz), 164.64(d,J＝25.7Hz),164.24(d,J＝26.0Hz),139.28,138.69,138.37,138.30, 133.54,133.22,132.39(d,J＝2.5Hz),132.08(d,J＝2.6Hz),131.06,130.98, 130.97,130.95,130.33,130.14,129.29,129.25,128.15(d,J＝2.3Hz),127.57(d, J＝2.7Hz),125.82,125.78,125.62,125.57,125.35,125.27,122.81,122.79, 122.64,102.68(d,J＝206.0Hz),102.52(d,J＝207.9Hz),63.10,62.87,52.84(d, J＝18.1Hz),52.77(d,J＝18.1Hz),26.88,26.86,14.20,13.81.19F NMR(376MHz,CDCl3,stereoisomeric mixture):δ-174.46,-174.98.IR(KBr):νmax(cm-1) ＝3061,2981,2936,1755,1735,1592,1566,1475,1445,1427,1356,1247,1203, 1136,1072,1015,967,860,779.HRMS(ESI-TOF)m/z calcd.for C21H19Br2FNaO3 +[M+Na]+:518.9577；found:518.9574.
实施例27
目标产物7：(E)-3,5-二(4-氯苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
白色固体，97％收率，熔点110.1-118.2℃，dr＝2.0:1，70％和63％ee[手性柱Daicel CHIRALCEL AD-H(0.46cm×25cm)；正己烷/异丙醇＝98/2；流速＝1.0mL/min；检测波长＝214nm；保留时间tR(major)＝33.907min,36.267 min；tR(minor)＝27.004min,29.496min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.35–7.24(m,12H), 6.53–6.23(m,3H),4.53(dd,J＝32.4,8.8Hz,1.5H),4.40–4.12(m,2H),4.07–4.01 (m,1H),2.31(d,J＝5.6Hz,1.5H),1.98(d,J＝5.5Hz,3H),1.25(t,J＝7.1Hz, 3H),1.06(t,J＝7.1Hz,1.5H).13C NMR(101MHz,CDCl3,stereoisomeric mixture):δ201.45(d,J＝29.7Hz),201.26(d,J＝29.8Hz),164.73(d,J＝25.7 Hz),164.35(d,J＝25.9Hz),135.64,134.99,134.80,134.72,133.83,133.76, 133.73,133.51,133.2,130.85(d,J＝2.3Hz),130.35(d,J＝2.6Hz),128.96, 128.90,128.79,128.77,127.73,127.71,125.03(d,J＝3.9Hz),124.93(d,J＝5.0 Hz),102.82(d,J＝205.8Hz),102.66(d,J＝207.5Hz),63.04,62.79,52.68(d,J＝ 18.2Hz),52.63(d,J＝18.2Hz),26.88,26.86,14.19,13.81.19F NMR(376MHz, CDCl3,stereoisomeric mixture):δ-174.72,-175.40.IR(KBr):νmax(cm-1)＝ 3033,2982,2921,2851,1754,1733,1594,1491,1412,1356,1247,1204,1092, 1014,970,818.HRMS(ESI-TOF)m/z calcd.for C21H19Cl2FNaO3 +[M+Na]+: 431.0587；found:431.0592.
实施例28
目标产物7：(E)-3,5-二(4-氟苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
无色油状物，65％收率，dr＝2.0:1，68％和67％ee[手性柱Daicel CHIRALCEL IG(0.46cm×25cm)；正己烷/异丙醇＝96/4；流速＝0.7mL/min；检测波长＝214nm；保留时间tR(major)＝20.727min,22.200min；tR(minor)＝ 15.773min,18.020min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.40–7.27(m,6H), 7.10–6.90(m,6H),6.54–6.18(m,3H),4.52(dd,J＝33.0,9.1Hz,1.5H),4.27(qd,J＝7.2,3.7Hz,2H),4.04(qd,J＝7.2,1.6Hz,1H),2.32(d,J＝5.7Hz,1.5H),1.96(d,J＝ 5.6Hz,3H),1.25(t,J＝7.2Hz,3H),1.05(t,J＝7.2Hz,1.5H).13C NMR(100MHz, CDCl3,stereoisomericmixture):δ201.65(d,J＝29.7Hz),201.38(d,J＝29.8Hz), 164.83(d,J＝25.7Hz),164.46(d,J＝25.9Hz),162.53(d,J＝247.5Hz),162.26(d,J ＝246.4Hz),133.32,133.09,132.55(d,J＝3.3Hz),132.47(d,J＝3.3Hz),132.37(d,J ＝3.4Hz),131.12(dd,J＝8.0,2.3Hz),130.63(dd,J＝8.0,2.7Hz),128.08(d,J＝8.1 Hz),128.05(d,J＝8.1Hz),124.36(dd,J＝3.5,2.2Hz),124.27(dd,J＝4.9,2.0Hz), 115.66(d,J＝21.3Hz),115.57(d,J＝21.3Hz),115.54(d,J＝21.7Hz),115.52(d,J＝ 21.7Hz),103.03(d,J＝205.6Hz),102.83(d,J＝207.2Hz),62.97,62.70,52.63(d,J＝ 18.2Hz),52.58(d,J＝18.2Hz),26.89,26.87,14.18,13.79.19F NMR(376MHz, CDCl3,stereoisomeric mixture):δ-113.69,-113.75,-114.28,-114.48,-175.00,-175.63. IR(KBr):νmax(cm-1)＝3042,2963,2927,2850,1755,1734,1602,1509,1417,1357, 1227,1159,1109,1016,970,913,823,803.HRMS(ESI-TOF)m/z calcd.for C21H19F3NaO3[M+Na]+:399.1179；found:399.1183.
实施例29
目标产物7：(E)-3,5-二(4-溴苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
白色固体，98％收率，熔点113.2-119.4℃，dr＝1.8:1，67％和62％ee[手性柱Daicel CHIRALCEL IF3+IG(0.46cm×25cm)；正己烷/异丙醇＝96/4；流速＝0.7mL/min；检测波长＝214nm；保留时间tR(major)＝38.473min,42.760 min；tR(minor)＝31.497min,32.417min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.55–7.13(m,12.5H), 6.60–6.14(m,3.1H),4.51(dd,J＝32.8,8.8,1.5H),4.33–4.20(m,2H),4.04(q,J＝ 7.1Hz,1H),2.31(d,J＝5.7Hz,1.7H),1.98(d,J＝5.6Hz,3H),1.25(t,J＝7.1 Hz,3H),1.06(t,J＝7.1Hz,1.7H).13C NMR(101MHz,CDCl3,stereoisomeric mixture):δ201.47(d,J＝29.8Hz),201.29(d,J＝29.8Hz),164.73(d,J＝25.7 Hz),164.36(d,J＝26.0Hz),136.09,135.44,135.20,135.13,133.61,133.36, 131.92,131.85,131.73,131.71,131.17(d,J＝2.2Hz),130.68(d,J＝2.6Hz), 128.03,128.01,125.05(d,J＝3.9Hz),124.94(d,J＝4.9Hz),122.00,121.93, 121.90,121.88,102.71(d,J＝205.8Hz),102.55(d,J＝207.5Hz),63.07,62.83, 52.74(d,J＝18.2Hz),52.68(d,J＝18.2Hz),26.88,26.85,14.18,13.79.19F NMR(376MHz,CDCl3,stereoisomeric mixture):δ-174.65,-175.34.IR (KBr):νmax(cm-1)＝3030,2962,2924,2853,1755,1732,1589,1487,1408,1356, 1245,1204,1072,1010,970,857,813.HRMS(ESI-TOF)m/z calcd.for C21H19Br2FNaO3 +[M+Na]+:518.9577；found:518.9572.
实施例30
目标产物7：(E)-3,5-二苯基-2-乙酰基-2-氟-4-戊烯酸乙酯
白色固体，62％收率，熔点78.7-83.3℃，dr＝2.2:1，77％和83％ee[手性柱DaicelCHIRALCEL AD-H(0.46cm×25cm)；正己烷/异丙醇＝98/2；流速＝ 1.0mL/min；检测波长＝214nm；保留时间tR(major)＝24.797min,38.728min； tR(minor)＝26.497min,49.438min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.42–7.21(m,15H), 6.61–6.32(m,3H),4.54(dd,J＝32.4,8.4Hz,1.5H),4.27(qd,J＝7.1,4.4Hz,2H), 4.02(q,J＝7.1Hz,1H),2.32(d,J＝5.6Hz,1.5H),1.93(d,J＝5.5Hz,3H),1.27 (t,J＝6.9Hz,3H),1.01(t,J＝7.1Hz,1.5H).13C NMR(101MHz,CDCl3, stereoisomeric mixture):δ201.90(d,J＝29.8Hz),201.64(d,J＝29.9Hz),165.03 (d,J＝25.8Hz),164.62(d,J＝26.1Hz),137.37,136.67,136.57,136.48,134.35, 134.17,129.52(d,J＝2.1Hz),129.00(d,J＝2.5Hz),128.76,128.67,128.57, 127.93,127.90,127.77,127.68,126.53,124.88(d,J＝5.0Hz),124.82(d,J＝5.2 Hz),103.18(d,J＝205.5Hz),102.95(d,J＝207.2Hz),62.90,62.59,53.71(d,J＝ 3.2Hz),53.53(d,J＝3.2Hz),27.01,26.94,14.22,13.76.19F NMR(376MHz,CDCl3,stereoisomeric mixture):δ-174.54,-175.26.IR(KBr):νmax(cm-1)＝ 3029,2982,2930,2852,1754,1733,1495,1453,1356,1247,1204,1133,1017, 968,913,747.HRMS(ESI-TOF)m/z calcd.for C21H21FNaO3 +[M+Na]+: 363.1367；found:363.1376.
实施例31
目标产物7：(E)-3,5-二(3-甲基苯基)-2-乙酰基-2-氟-4-戊烯酸乙酯
无色油状物，52％收率，dr＝1.6:1，77％和70％ee[手性柱Daicel CHIRALCEL IF3+IG(0.46cm×25cm)；正己烷/异丙醇＝96/4；流速＝0.7 mL/min；检测波长＝214nm；保留时间tR(major)＝34.823min,35.763min；tR (minor)＝26.687min,37.647min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ7.35–6.99(m,13H), 6.60–6.27(m,3.3H),4.48(dd,J＝32.6,8.7Hz,1.6H),4.35–4.22(m,2H), 4.09–3.97(m,1.3H),2.35(d,J＝5.6Hz,1.8H),2.34–2.29(m,10H),1.94(d,J＝ 5.6Hz,3H),1.27(t,J＝7.1Hz,3H),1.03(t,J＝7.1Hz,1.8H).13C NMR(101 MHz,CDCl3,stereoisomeric mixture):δ201.94(d,J＝29.8Hz),201.70(d,J＝ 29.9Hz),165.10(d,J＝25.9Hz),164.67(d,J＝26.2Hz),138.34,138.16,138.12, 138.11,137.30,136.65,136.57,136.47,134.32,134.10,130.23(d,J＝1.9Hz), 129.72(d,J＝2.3),128.69,128.65,128.60,128.53,128.47,128.45,128.37, 127.17,127.12,126.42(d,J＝2.4Hz),125.97(d,J＝2.5Hz),124.80,124.76, 124.70,124.64,123.77,123.74,103.23(d,J＝205.4Hz),102.99(d,J＝207.2Hz), 62.86,62.53,52.65(d,J＝18.1Hz),27.04,27.00,21.50,21.38,21.37,14.22,13.76.19F NMR(376MHz,CDCl3,stereoisomeric mixture):δ-174.47,-175.08. IR(KBr):νmax(cm-1)＝3029,2981,2922,2868,1755,1733,1605,1489,1446, 1403,1356,1238,1200,1133,1096,1018,967,858,780.HRMS(ESI-TOF)m/z calcd.for C23H25FNaO3 +[M+Na]+:391.1680；found:391.1683.
实施例32
目标产物7：(E)-3,5-二(2-萘基)-2-乙酰基-2-氟-4-戊烯酸乙酯
白色固体，91％收率，熔点141.8-149.7℃，dr＝1.8:1，61％和67％ee[手性柱Daicel CHIRALCEL AD-H(0.46cm×25cm)；正己烷/异丙醇＝98/2；流速＝1.0mL/min；检测波长＝214nm；保留时间tR(major)＝57.154min,69.932 min；tR(minor)＝49.735min,60.029min]。
1H NMR(400MHz,CDCl3,stereoisomeric mixture):δ8.01–7.30(m,21.8H), 6.86–6.48(m,3.1H),4.78(dd,J＝33.2,8.7Hz,1.6H),4.36–4.25(m,2H),3.99 (qd,J＝7.1,2.2Hz,1.1H),2.37(d,J＝5.7Hz,1.7H),1.94(d,J＝5.6Hz,3H), 1.28(t,J＝7.1Hz,3H),0.95(t,J＝7.1Hz,1.7H).13C NMR(101MHz,CDCl3, stereoisomeric mixture):δ201.85(d,J＝29.7Hz),201.73(d,J＝30.0Hz),165.10 (d,J＝25.7Hz),164.66(d,J＝26.1Hz),134.88,134.70,134.50,134.19,134.00, 133.89,133.51,133.49,133.43,133.39,133.13,132.78,128.75,128.49,128.42, 128.26,128.25,128.10,128.04,128.01,127.97,127.94,127.22(d,J＝2.6Hz), 127.04(d,J＝2.7Hz),126.73,126.62,126.38,126.37,126.31,126.27,126.25, 126.13,126.09,126.07,125.20,125.16,125.12,125.07,123.55,123.47,103.35(d, J＝205.5Hz),103.16(d,J＝207.3Hz),63.02,62.67,53.78(d,J＝18.1Hz), 53.74(d,J＝18.1Hz),27.06,27.03,14.27,13.78.19F NMR(376MHz,CDCl3, stereoisomeric mixture):δ-174.01,-174.75.IR(KBr):νmax(cm-1)＝3056,2981,2929,2852,1754,1732,1598,1508,1416,1356,1244,1203,1124,1096,1017, 966,912,859,814,743.HRMS(ESI-TOF)m/z calcd.for C29H25FNaO3 + [M+Na]+:463.1680；found:463.1684.
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (9)

1.一种手性亚磺酰胺配体类化合物，其特征在于，该类化合物的分子式如下：
其中*为手性原子，R为氢。
2.一种如权利要求1所述的手性亚磺酰胺配体类化合物的制备方法，其特征在于，该方法包括以下步骤：
氩气保护下，在反应管中加入原料水杨酸和干燥的四氢呋喃，分批加入碳酰二咪唑，反应释放出CO2，室温搅拌0.5小时后升温至50℃继续搅拌1小时后结束反应，将反应液冷却至室温，浓缩得活性中间体，直接用于下一步反应；
在制备活性中间体同时，另备干燥的反应管，加入手性叔丁基亚磺酰胺和干燥的四氢呋喃，加入氢化钾，室温下搅拌0.5小时后加入活性中间体，继续搅拌2小时后，加入1M HCl淬灭反应至弱酸性，乙酸乙酯萃取，饱和食盐水洗涤，无水硫酸钠干燥，过滤，滤液旋干得粗品，硅胶柱层析纯化制备得手性亚磺酰胺配体类化合物。
3.根据权利要求2所述的一种手性亚磺酰胺配体类化合物的制备方法，其特征在于，所述的水杨酸、碳酰二咪唑、叔丁基亚磺酰胺、氢化钾的摩尔比为1:1:1:2。
4.根据权利要求2所述的一种手性亚磺酰胺配体类化合物的制备方法，其特征在于，所述的氢化钾为分散于矿物油中的30％悬浮液。
5.根据权利要求2所述的一种手性亚磺酰胺配体类化合物的制备方法，其特征在于，制得的手性亚磺酰胺配体类化合物需要经过重结晶、薄层层析或者柱层析的分离。
6.根据权利要求1所述的一种手性亚磺酰胺配体类化合物的用途，其特征在于，应用在过渡金属钯催化的不对称烯丙基化反应中；该反应步骤如下：
在有机溶剂中，以对称烯丙基醋酸酯化合物和2-氟乙酰乙酸乙酯为原料，以[Pd(C3H5)Cl]2与手性亚磺酰胺配体作为催化剂，在添加剂的作用下反应12～24小时制得(E)-3,5-二芳基-2-乙酰基-2-氟-4-戊烯酸乙酯类化合物。
7.根据权利要求6所述的一种手性亚磺酰胺配体类化合物的用途，其特征在于，所述的对称烯丙基醋酸酯化合物、2-氟乙酰乙酸乙酯、[Pd(C3H5)Cl]2、手性亚磺酰胺配体、添加剂的摩尔比为1:3:0.04:0.08:3。
8.根据权利要求6所述的一种手性亚磺酰胺配体类化合物的用途，其特征在于，所述的对称烯丙基醋酸酯的结构式为：其中R1选自芳基；
所述的2-氟乙酰乙酸乙酯的结构式为：
所述的(E)-3,5-二芳基-2-乙酰基-2-氟-4-戊烯酸乙酯类化合物的结构式为：其中R1选自芳基。
9.根据权利要求6所述的一种手性亚磺酰胺配体类化合物的用途，其特征在于，所述的反应温度选自0℃～25℃。
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