專利名稱：一種具有多種手性中心的二茂鐵噁唑啉膦配體合成方法及用途的制作方法
技術(shù)領(lǐng)域：
本發(fā)明涉及一類手性配體、合成方法及用途，即一種具有多種手性中心的二茂鐵噁唑啉膦配體、合成方法及用途。
手性噁唑啉膦配體是一類重要的手性配體，G.Helmchen和A.Pfaltz在Acc.Chem.Res.2000,33,336中公開了苯環(huán)衍生的噁唑啉膦配體(PHOX)在不對(duì)稱催化反應(yīng)中的應(yīng)用。盡管他們這種配體在烯丙基胺化，烯丙基烷基化反應(yīng)中產(chǎn)物的產(chǎn)率和對(duì)映選擇性都比較好，但是對(duì)于區(qū)域選擇性的烯丙基化的反應(yīng)及Heck反應(yīng)則不是很令人滿意，而且對(duì)于工業(yè)上應(yīng)用意義較大的氫化反應(yīng)，硅氫化反應(yīng)等結(jié)果也還很不理想。為此尋找新的手性配體使之適用于一些反應(yīng)或更多反應(yīng)并能有高的催化活性及對(duì)映選擇性一直是化學(xué)工作者的研究熱點(diǎn)之一。
本發(fā)明的目的之一就是提供一種具有多種手性中心的二茂鐵噁唑啉膦配體。
本發(fā)明的目的之二是提供該種二茂鐵噁唑啉膦配體的合成方法。
本發(fā)明的目的之三是提供該種二茂鐵噁唑啉膦配體的用途。
本發(fā)明提供了一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式是 其中R=苯基、萘基或1-8個(gè)碳的烷基R′=苯基、萘基或1-8個(gè)碳的烷基R″=5-32個(gè)碳的烷基或芳基X=NH、O、S具體來說可以是 這類配體中R=苯基、萘基或1-8個(gè)碳的烷基取代基；R’=苯基、萘基或1-8個(gè)碳的烷基取代基；R″=5-32個(gè)碳的烷基或芳基；X=NH、O或S。一般來說，上述配體中的P和N上具有中心手性，HX R″X具有軸手性或中心手性。
本發(fā)明的化合物的合成方法是由二(二胺基)膦取代的二茂鐵噁唑啉與分子通式為HXR″XH的手性化合物反應(yīng)制得，反應(yīng)中還可加入催化劑。其反應(yīng)式如下 用結(jié)構(gòu)式可表述為 具體的合成步驟是在有機(jī)溶劑中和0-150℃的溫度條件下，二(二胺基)膦取代的二茂鐵-4-取代的噁唑啉與分子通式HXR″XH的手性化合物及催化劑的摩爾比依次為1∶0.8-5∶0-0.2，反應(yīng)1-50小時(shí)。反應(yīng)溫度越低，反應(yīng)時(shí)間越長(zhǎng)。所述的二(二胺基)膦取代的二茂鐵-4-取代的噁唑啉具有分子通式是 式中R、R′如前所述，HXR”XH是5-32個(gè)碳的手性二醇、手性二胺、手性二酚、手性二硫醇或手性二硫酚，例如聯(lián)二萘酚、帶有取代基的聯(lián)二萘酚、聯(lián)二萘胺、聯(lián)二萘硫酚等，上述R”、X如前所述。在不加催化劑的條件下，反應(yīng)仍可進(jìn)行。所述的有機(jī)溶劑為極性或非極性溶劑，如苯、四氯化碳、四氫呋喃、乙醚、二氯甲烷、甲苯、環(huán)己烷、石油醚、丙酮、吡啶、CHCl3、正己烷、正庚烷、二氧六環(huán)等。所述的催化劑為氮原子上含有孤對(duì)電子的有機(jī)胺化合物，如四甲基二乙胺、聯(lián)二吡啶、三辛胺、對(duì)二甲胺基吡啶，三乙胺，二異丙基乙基胺等。該配體制備過程中會(huì)再生一個(gè)手性的膦。反應(yīng)產(chǎn)生的異構(gòu)體通?？梢杂弥鶎游龌蛑亟Y(jié)晶的方法順利分開。反應(yīng)產(chǎn)物即本發(fā)明的一種具有多種手性中心的二茂鐵噁唑啉膦配體。
本發(fā)明還提供了此目標(biāo)化合物-二茂鐵噁唑啉膦配體的用途，即應(yīng)用在鈀催化烯丙基化反應(yīng)中，用各種烯丙基醋酸酯或碳酸酯作為底物，利用丙二酸衍生物及各種胺類化合物作為親核試劑時(shí)，可以得到具有手性的烯丙基羧酸或氨基衍生物。
本發(fā)明提供了一種全新的配體，該配體的合成方法簡(jiǎn)便、條件溫和，適于工業(yè)化。該配體用于制備具有手性的烯丙基羧酸或氨基衍生物，與現(xiàn)有的技術(shù)相比，反應(yīng)速率、產(chǎn)率、對(duì)映選擇性及區(qū)域選擇性都好，并且由于它們具有二茂鐵骨架及多手性中心的特點(diǎn)，在過渡金屬催化的不對(duì)稱反應(yīng)中具有很高的催化活性和手性誘導(dǎo)效果，而且有很強(qiáng)的調(diào)節(jié)能力。上述特點(diǎn)可以用以下實(shí)例給予說明，當(dāng)R=-CH2CH3，R’=-CH(CH3)3，和光學(xué)純的反式環(huán)己二醇反應(yīng)時(shí)，有三個(gè)手性中心，共有8個(gè)配體，如下 這類配體很可能在氫化，硅氫化等不對(duì)稱催化反應(yīng)中有較好的應(yīng)用前景。
以下實(shí)施例有助于理解本發(fā)明，但不限于本發(fā)明的內(nèi)容。
實(shí)施例一(構(gòu)型為R=C2H5；R’=i-CH(CH3)2；R”XH=聯(lián)二萘酚)室溫，471mg(1mmol)(S)-二(二乙基胺基)膦二茂鐵唑啉1(R=C2H5；R’=i-CH(CH3)2)，286-572mg(1-2mmol)(R)-聯(lián)萘酚，催化量的對(duì)二甲胺基吡啶或四甲基二乙胺(5％)溶于5mL乙醚或四氫呋喃中，所得的黃色溶液在20-40℃反應(yīng)10-48小時(shí)，TLC跟蹤至反應(yīng)結(jié)束，用水洗，飽和食鹽水洗，無水硫酸鈉干燥，減壓除去溶劑，柱層析純化，得到兩個(gè)橙黃色固體588mg，總產(chǎn)率為86％。P1(S,SPhos，RA，R=-C2H5；R’=-CH(CH3)2；R”XH=聯(lián)二萘酚)mp 136-138℃；[α]D25=-410°(c,0.37,CHCl3)；1H NMRδ7.83-8.06(m,5H),7.21-7.37(m,7H),5.21(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；31P NMR(161.92 MHz,CDCl3)δ127.87；MS m/z 684(M+,5),611(65),541(100),399(28),286(17)；IR(KBr)3056,2960,1645,1506,1465,1237,1127；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,69.82；H,6.14；N,3.87.P2(S,RPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH=聯(lián)二萘酚)橙色固體mp 99-101℃；[α]D25=493°(c,0.54,CHCl3)；1H NMRδ9.90(br,1H),7.79-7.99(m,5H),7.12-7.41(m,7H),5.17(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.06(m,1H),4.00(m,1H),3.77(m,1H),2.38-2.61(m,4H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.50(t,J=6.9 Hz,6H)；31P NMR(161.92 MHz,CDCl3)δ117.94；MS m/z 684(M+,8),611(48),540(100),399(85),313(33),286(65)；IR(KBr)3051,2962,1640,1589,1461,1232,1024,810；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.34；H,6.31；N,3.83.
同以上條件，從各種二(二胺基)膦取代的二茂鐵噁唑啉出發(fā)，和各種手性二醇，手性二胺或手性二酚等在催化劑的催化下可以得到大量的配體。其數(shù)據(jù)如下P3(S,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=聯(lián)二萘酚)；1H NMRδ7.80-8.09(m,5H),7.19-7.39(m,7H),5.22(br,1H),4.45(m,1H),4.39(m,1H),4.23(dd,J=8.6,9.1 Hz,1H),4.12(s,1H),4.09(s,1H),3.89-4.03(m,4H),3.73(m,1H),3.35(s,1H),2.87(t,J=7.5 Hz,4H),1.82(m,1H),0.97(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,31),0.74(t,J=7.0 Hz,6H)；MS m/z 684IR(KBr)3054,2965,1644,1502,1466,1240,1126；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,69.99；H,6.11；N,3.89.P4(S,SPhos,SA,R=-C2H5；R’=-CH(CH3)2R”XH=聯(lián)二萘酚)；1H NMRδ9.90(br,1H),7.78-7.99(m,5H),7.10-7.41(m,7H),5.16(t,J=1.2 Hz,1H),4.55(t,J=1.1 Hz,1H),4.31-4.40(m,4H),4.21-4.26(m,1H),4.12(t,J=8.0 Hz,1H),4.07(m,1H),4.00(m,1H),3.78(m,1H),2.35-2.60(m,4H),1.83(m,1H),1.01(d,J=6.7 Hz,3H),0.91(d,J=6.7 Hz,3H),0.50(t,J=6.9 Hz,6H)；MS m/z 684；286；IR(KBr)3055,2968,1641,1586,1460,1230,1023；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.14；H,6.03；N,3.99.P5(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=聯(lián)二萘酚)；1H NMRδ7.83-8.09(m,5H),7.23-7.39(m,7H),5.24(br,1H),4.54(m,1H),4.41(m,1H),4.23(dd,J=8.5,9.2 Hz,1H),4.14(s,1H),4.07(s,1H),3.89-4.03(m,4H),3.73(m,1H),3.37(s,1H),2.85(t,J=7.5 Hz,4H),1.83(m,1H),0.97(d,J=6.8 Hz,3H),0.92(d,J=6.8 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 684,541,286；IR(KBr)3050,2964,1643,1500,1468,1239,1123；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,69.88；H,6.10；N,3.94.P6(R,SPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=聯(lián)二萘酚)；1H NMRδ9.90(br,1H),7.75-7.98(m,5H),7.10-7.41(m,7H),5.15(t,J=1.2 Hz,1H),4.55(t,J=1.1 Hz,1H),4.34-4.45(m,4H),4.21-4.26(m,1H),4.10(t,J=8.0 Hz,1H),4.07(m,1H),4.01(m,1H),3.79(m,1H),2.39-2.60(m,4H),1.85(m,1H),0.99(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.51(t,J=6.8 Hz,6H)；MS m/z 684,611,286；IR(KBr)3050,2964,1642,1582,1463,1234,1021；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.21；H,6.07；N,3.91.P7(R,RPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=聯(lián)二萘酚)；1H NMRδ7.83-8.05(m,5H),7.21-7.39(m,7H),5.20(br,1H),4.54(m,1H),4.39(m,1H),4.21(dd,J=8.5,9.2 Hz,1H),4.14(s,1H),4.09(s,1H),3.89-4.03(m,4H),3.74(m,1H),3.36(s,1H),2.87(t,J=7.5 Hz,4H),1.83(m,1H),0.97(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=6.7 Hz,6H)；MS m/z 684,611,541,286；IR(KBr)3052,2962,1641,1504,1467,1236,1123；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,7.32；H,6.18；N,3.89.P8(R,SPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=聯(lián)二萘酚)；1H NMRδ9.93(br,1H),7.79-8.09(m,5H),7.12-7.45(m,7H),5.15(t,J=1.2 Hz,1H),4.56(t,J=1.1 Hz,1H),4.30-4.45(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.05(m,1H),4.02(m,1H),3.78(m,1H),2.38-2.56(m,4H),1.85(m,1H),1.01(d,J=6.8 Hz,3H),0.93(d,J=6.7 Hz,3H),0.49(t,J=6.9 Hz,6H)；MS m/z 684,611,286；IR(KBr)3049,2960,1639,1589,1461,1232,1023；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.38；H,6.20；N,4.31.P9(S,SPhos,RA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ7.85-8.05(m,5H),7.21-7.37(m,7H),5.22(br,1H),4.54(t,J=1.2 Hz,1H),4.39(t,J=1.2 Hz,1H),4.08-4.20(m,4H),3.97(m,1H),3.89(m,1H),3.84(dd,J=7.7,10.0 Hz,1H),3.70(m,1H),3.37(m,1H),2.85(m,4H),0.93(s,9H),0.75(t,J=7.1 Hz,6H)；MS m/z 698,625,413,313,242；IR(KBr)3541,3055,2964,1648,1589,1505,1459,1123；元素分析C41H43N2O3PFe計(jì)算值C,70.69；H,6.17；N,4.02；實(shí)測(cè)值C,70.96；H,6.29；N,3.95.P10(S,RPhos,RA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ8.89(br,1H),7.79-8.01(m,5H),7.12-7.35(m,12H),5.45(dd,J=8.3,9.6 Hz,1H),5.17(s,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.68(s,1H),4.48(m,1H),4.36(m,2H),4.19(t,J=8.1 Hz,1H),4.08-4.11(m,2H),3.80(s,1H),2.63-2.41(m,4H),0.53(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3109,2927,1639,1590,1504,1457,1263,1129；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.69；H,5.77；N,3.66.P11(S,RPhos,SA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ7.79-8.04(m,5H),7.12-7.38(m,12H),5.44(dd,J=8.3,9.8 Hz,1H),5.22(br,1H),5.16(s,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.69(s,1H),4.52(m,1H),4.38(m,2H),4.21(t,J=8.1 Hz,1H),4.08-4.13(m,2H),3.81(s,1H),2.63-2.42(m,4H),0.75(t,J=7.0 Hz,6H)；MS m/z 643,541,286；IR(KBr)3112,2926,1639,1593,1502,1455,1263；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.79；H,5.57；N,3.76.P12(S,SPhos,SA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ9.92(br,1H),7.79-8.03(m,5H),7.12-7.38(m,12H),5.44(dd,J=8.3,9.7 Hz,1H),5.16(s,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.67(s,1H),4.45(m,1H),4.34(m,2H),4.17(t,J=8.1 Hz,1H),4.07-4.13(m,2H),3.82(s,1H),2.61-2.40(m,4H),0.50(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3109,2926,1639,1591,1504,1459,1265,1129；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.88；H,5.52；N,3.69.P13(R,RPhos,SA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ7.79-8.01(m,5H),7.12-7.34(m,12H),5.44(dd,J=8.3,9.6 Hz,1H),5.22(br,1H),5.16(s,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.70(s,1H),4.45(m,1H),4.37(m,2H),4.189(t,J=8.1 Hz,1H),4.08-4.11(m,2H),3.83(s,1H),2.63-2.40(m,4H),0.74(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3107,2926,1637,1591,1503,1455,1263,1127；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.4 3；N,3.90；實(shí)測(cè)值C,71.99；H,5.49；N,3.75.P14(R,SPhos,SA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ8.96(br,1H),7.74-8.03(m,5H),7.11-7.33(m,12H),5.42(dd,J=8.3,9.9 Hz,1H),5.15(s,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.69(s,1H),4.52(m,1H),4.39(m,2H),4.18(t,J=8.1 Hz,1H),4.08-4.13(m,2H),3.83(s,1H),2.63-2.42(m,4H),0.54(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3109,2927,1642,1589,1502,1457,1263,1126；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.82；H,5.58；N,3.92.P15(R,SPhos,RA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ7.79-8.04(m,5H),7.12-7.36(m,12H),5.43(dd,J=8.3,9.6 Hz,1H),5.23(br,1H),5.17(s,1H),4.75(dd,J=8.6,9.8 Hz,1H),4.69(s,1H),4.49(m,1H),4.38(m,2H),4.19(t,J=8.1 Hz,1H),4.08-4.11(m,2H),3.82(s,1H),2.63-2.43(m,4H),0.75(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3111,2928,1640,1590,1504,1459,1263,1127元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.76；H,5.62；N,3.82.P16(R,RPhos,RA,R=C2H5；R’=-C(CH3)3；R”XH=聯(lián)二萘酚)1H NMRδ9.01(br,1H),7.79-8.01(m,5H),7.11-7.35(m,12H),5.46(dd,J=8.3,9.6 Hz,1H),5.16(s,1H),4.77(dd,J=8.6,9.8 Hz,1H),4.69(s,1H),4.50(m,1H),4.37(m,2H),4.20(t,J=8.1 Hz,1H),4.08-4.13(m,2H),3.80(s,1H),2.63-2.41(m,4H),0.53(t,J=7.0 Hz,6H)；MS m/z 643,435,286；IR(KBr)3109,2927,1640,1593,1502,1457,1263,1125；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.77；H,5.67；N,3.75.P17(S,SPhos,RA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ8.89(br,1H),7.79-8.01(m,5H),7.1 2-7.35(m,12H),5.45(dd,J=8.3,9.6 Hz,1H),5.17(6,1H),4.76(dd,J=8.6,9.8 Hz,1H),4.68(s,1H),4.48(m,1H),4.36(m,2H),4.19(t,J=8.1 Hz,1H),4.08-4.11(m,2H),3.80(s,1H),2.63-2.41(m,4H),0.53(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3109,2927,1639,1590,1504,1457,1263,1129；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.69；H,5.77；N,3.66.P18(S,RPhos,RA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.81-8.05(m,5H),7.22-7.41(m,12H),5.18(dd,J=8.0,9.9 Hz,1H),4.62(t,J=8.3,9.9 Hz,1H),4.60(m,1H),4.48(m,1H),4.20-4.11(m,3H),4.01(m,1H),3.90(m,1H),3.77(m,1H),3.41(m,1H),2.80-2.88(m,4H),2.04(br,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3056,2966,1641,1590,1503,1461,1232,1125,1024；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.73；H,5.68；N,3.84.P19(S,RPhos,SA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ8.91(br,1H),7.81-8.06(m,5H),7.22-7.43(m,12H),5.18(dd,J=8.0,9.9 Hz,1H),4.62(t,J=8.3,9.9 Hz,1H),4.60(m,1H),4.48(m,1H),4.20-4.13(m,3H),4.02(m,1H),3.91(m,1H),3.78(m,1H),3.41(m,1H),2.80-2.89(m,4H),0.49(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3050,2969,1644,1592,1463,1231,1125；Anal.Calc.For C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.83；H,5.65；N,3.86.P20(S,SPhos,SA,R=C2H5；R’=-C6H5,R”XH=聯(lián)二萘酚)1H NMRδ7.81-8.05(m,5H),7.22-7.42(m,12H),5.17(dd,J=8.0,9.9 Hz,1H),4.63(t,J=8.3,9.9 Hz,1H),4.60(m,1H),4.48(m,1H),4.20-4.12(m,3H),4.03(m,1H),3.91(m,1H),3.75(m,1H),3.41(m,1H),2.80-2.88(m,4H),2.09(br,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3056,2966,1640,1592,1500,1024；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.99；H,5.59；N,3.74.P21(R,RPhos,SA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ8.92(br,1H),7.81-8.02(m,5H),7.20-7.41(m,12H),5.17(dd,J=8.0,9.9 Hz,1H),4.61(t,J=8.3,9.9 Hz,1H),4.60(m,1H),4.50(m,1H),4.22-4.11(m,3H),4.02(m,1H),3.91(m,1H),3.78(m,1H),3.41(m,1H),2.80-2.88(m,4H),0.50(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3056,2966,1642,1590,1501,1461,1232,1125,1024；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.76；H,5.62；N,3.77.P22(R,SPhos,SA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.81-8.05(m,5H),7.22-7.41(m,12H),5.17(dd,J=8.0,9.9 Hz,1H),4.64(t,J=8.3,9.9 Hz,1H),4.60(m,1H),4.48(m,1H),4.20-4.11(m,3H),4.01(m,1H),3.90(m,1H),3.77(m,1H),3.41(m,1H),2.80-2.88(m,4H),2.06(br,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3056,2966,1640,1591,1503,1232,1125；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.69；H,5.70；N,3.96.P23(R,SPhos,RA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ8.93(br,1H),7.80-8.05(m,5H),7.22-7.41(m,12H),5.18(dd,J=8.0,9.9 Hz,1H),4.63(t,J=8.3,9.9 Hz,1H),4.61(m,1H),4.49(m,1H),4.20-4.11(m,3H),4.02(m,1H),3.91(m,1H),3.77(m,1H),3.41(m,1H),2.80-2.88(m,4H),0.49(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3056,2969,1641,1590,1464,1232,1024；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.75；H,5.69；N,3.73.P24(R,RPhos,RA,R=C2H5；R’=-C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.81-8.04(m,5H),7.22-7.41(m,12H),5.20(dd,J=8.0,9.9 Hz,1H),4.64(t,J=8.3,9.9 Hz,1H),4.61(m,1H),4.48(m,1H),4.20-4.13(m,3H),4.02(m,1H),3.91(m,1H),3.77(m,1H),3.41(m,1H),2.80-2.89(m,4H),2.04(br,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 643,541,435,286；IR(KBr)3055,2967,1641,1594,1503,1461；元素分析C43H39N2O3PFe計(jì)算值C,71.93；H,5.43；N,3.90；實(shí)測(cè)值C,71.83；H,5.68；N,3.79.P25(S,SPhos,RA,R=C2H5；R’=CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ9.25(br,1H),7.79-8.03(m,5H),7.11-7.41(m,12H),5.09(t,J=1.2 Hz,1H),4.59-4.64(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.33(m,3H),4.07(dd,J=7.2,8.1 Hz,1H),3.92(m,1H),3.74(m,1H),3.17(dd,J=5.0,13.7 Hz,1H),2.67(dd,J=8.9,13.8 Hz,1H),2.41-2.62(m,4H),0.53(t,J=7.0 Hz,6H)；MS m/z 732,659,541,447,315,286；IR(KBr)3055,2967,1639,1589,1504,1461,1232,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,72.00；H,5.66；N,3.85.P26(S,RPhos,RA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.82-8.05(m,5H),7.21-7.39(m,12H),5.24(br,1H),4.52(m,1H),4.34-4.42(m,2H),4.18(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.01(t,J=7.8 Hz,1H),3.94(m,1H),3.88(m,1H),3.73(m,1H),3.39(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.67(dd,J=9.1,13.7 Hz,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 732,659,541,447,315,286；IR(KBr)3055,2966,1641,1588,1504,1458,1226,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.73；H,5.94；N,3.69.P27(S,RPhos,SA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ9.25(br,1H),7.82-8.04(m,5H),7.21-7.39(m,12H),4.52(m,1H),4.34-4.42(m,2H),4.17(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.02(t,J=7.8 Hz,1H),3.94(m,1H),3.88(m,1H),3.74(m,1H),3.39(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.87(m,4H),2.67(dd,J=9.1,13.7 Hz,1H),0.51(t,J=7.0 Hz,6H)；MS m/z 732,541,286；IR(KBr)3055,2966,1640,1589,1504,1458,1226,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.93；H,5.89；N,3.78.P28(S,SPhos,SA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.81-8.05(m,5H),7.21-7.39(m,12H),5.26(br,1H),4.52(m,1H),4.34-4.44(m,2H),4.18(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.01(t,J=7.8 Hz,1H),3.94(m,1H),3.88(m,1H),3.74(m,1H),3.39(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.67(dd,J=9.1,13.7 Hz,1H),0.73(t,J=7.0 Hz,6H)；MS m/z 732,541,286；IR(KBr)3055,2966,1641,1587,1504,1458,1225,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.99；H,5.79；N,3.77.P29(R,RPhos,SA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ9.22(br,1H),7.82-8.05(m,5H),7.21-7.37(m,12H),4.54(m,1H),4.34-4.42(m,2H),4.18(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.01(t,J=7.8 Hz,1H),3.95(m,1H),3.88(m,1H),3.73(m,1H),3.38(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.66(dd,J=9.1,13.7 Hz,1H),0.52(t,J=7.0 Hz,6H)；MS m/z 732,659,541,286；IR(KBr)3054,2966,1640,1588,1502,1458,1226,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.99；H,5.81；N,3.67.P30(R,SPhos,SA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.82-8.06(m,5H),7.25-7.39(m,12H),5.25(br,1H),4.53(m,1H),4.34-4.42(m,2H),4.18(t,J=8.6 Hz,1H),4.05-4.15(m,2H),),4.03(t,J=7.8 Hz,1H),3.95(m,1H),3.88(m,1H),3.73(m,1H),3.39(m,1H),3.19(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.66(dd,J=9.1,13.7 Hz,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 732,659,541,286；IR(KBr)3055,2966,1641,1590,1458,1226,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.94；H,5.72；N,3.99.P31(R,SPhos,RA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ9.23(br,1H),7.82-8.05(m,5H),7.21-7.39(m,12H),4.53(m,1H),4.34-4.45(m,2H),4.19(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.01(t,J=7.8 Hz,1H),3.94(m,1H),3.88(m,1H),3.75(m,1H),3.39(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.66(dd,J=9.1,13.7 Hz,1H),0.52(t,J=7.0 Hz,6H)；MS m/z 732,659,541,286；IR(KBr)3055,2968,1640,1588,1504,1459,1228,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,72.00；H,5.71；N,3.82.P32(R,RPhos,RA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)1H NMRδ7.82-8.07(m,5H),7.21-7.41(m,12H),5.25(br,1H),4.52(m,1H),4.34-4.42(m,2H),4.18(t,J=8.6 Hz,1H),4.05-4.13(m,2H),),4.01(t,J=7.8 Hz,1H),3.92(m,1H),3.89(m,1H),3.75(m,1H),3.40(m,1H),3.18(dd,J=4.7,13.7 Hz,1H),2.86(m,4H),2.68(dd,J=9.1,13.7 Hz,1H),0.76(t,J=7.0 Hz,6H)；MS m/z 732,541,447,315,286；IR(KBr)3055,2966,1641,1588,1504,1023；元素分析C44H41N2O3PFe計(jì)算值C,72.19；H,5.60；N,3.83；實(shí)測(cè)值C,71.93；H,5.74；N,3.76.P33(S,SPhos,RA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ7.83-8.06(m,5H),7.21-7.37(m,5H),5.21(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.25(s,6H),1.82(m,1H),0.98(d,J=6.8Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 684,611,286；IR(KBr)3056,2960,1645,1506,1465,1237,1127；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,69.88；H,6.14；N,3.87.P34(S,RPhos,RA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ9.90(br,1H),7.79-7.99(m,5H),7.12-7.41(m,5H),5.17(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.06(m,1H),4.00(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.50(t,J=6.9 Hz,6H)；MS m/z 684,611,399,313,286；IR(KBr)3051,2962,1640,1590,1461,1232,1024,810；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.34；H,6.31；N,3.93.P35(S,RPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ7.78-7.98(m,5H),7.12-7.41(m,5H),5.21(br,1H),5.17(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.07(m,1H),4.00(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.75(t,J=6.9 Hz,6H)；MS m/z 684,611,540,399,313,286；IR(KBr)3051,2962,1641,1589,1462；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.19；H,6.20；N,3.93.P36(S,SPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ9.90(br,1H),7.79-7.99(m,5H),7.12-7.41(m,5H),5.17(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.45(m,4H),4.21-4.26(m,1H),4.12(t,J=8.0 Hz,1H),4.06(m,1H),4.00(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.01(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.50(t,J=6.9 Hz,6H)；MS m/z 684,611,540,286；IR(KBr)3051,2962,1642,1589,1462,1232；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.44；H,5.97；N,4.01.P37(R,RPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ7.79-7.99(m,5H),7.11-7.43(m,5H),5.21(br,1H),5.17(t,J=1.2 Hz,1H),4.58(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.06(m,1H),4.00(m,1H),3.79(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.92(d,J=6.7 Hz,3H),0.75(t,J=6.9 Hz,6H)；MS m/z 684,611,313,286；IR(KBr)3050,2962,1640,1589,1461,1232,1024,810；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.21；H,6.11；N,3.92.P38(R,SPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ9.92(br,1H),7.79-7.99(m,5H),7.12-7.41(m,5H),5.18(t,J=1.2 Hz,1H),4.55(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.06(m,1H),4.02(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.93(d,J=6.7 Hz,3H),0.50(t,J=6.9 Hz,6H)；MS m/z 684,540,399,313,286；IR(KBr)3052,2962,1640,1589,1460,1232,1024；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.28；H,6.14；N,3.85.P39(R,RPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ7.79-7.95(m,5H),7.12-7.41(m,5H),5.21(br,1H),5.17(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.05(m,1H),4.00(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.90(d,J=6.7 Hz,3H),0.74(t,J=6.9 Hz,6H)；MS m/z 684,611,399,286；IR(KBr)3051,2964,1640,1589,1461,1233,1023；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.17；H,6.01；N,3.99.P40(R,SPhos,SA,R=-CH3；R’=i-CH(CH3)2；R”XH=3,3-二甲基聯(lián)二萘酚)；1H NMRδ9.91(br,1H),7.79-7.99(m,5H),7.10-7.42(m,5H),5.18(t,J=1.2 Hz,1H),4.57(t,J=1.1 Hz,1H),4.31-4.43(m,4H),4.20-4.26(m,1H),4.11(t,J=8.0 Hz,1H),4.07(m,1H),4.02(m,1H),3.77(m,1H),2.38-2.61(m,4H),2.21(s,6H),1.84(m,1H),1.00(d,J=6.8 Hz,3H),0.90(d,J=6.7 Hz,3H),0.52(t,J=6.9 Hz,6H)；MS m/z 684,611,540,399,313,286；IR(KBr)3049,2962,1642,1589,1462,1232；元素分析C40H41N2O3PFe計(jì)算值C,70.18；H,5.99；N,4.09；實(shí)測(cè)值C,70.14；H,6.25；N,4.11.P41(S,SPhos,RA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.37(m,22H),5.21(br,3H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),1.52(m,3H)；MS m/z 750,611,541,399,286；IR(KBr)3440,3056,2960,1645,1506,1465,1237,1127；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.55；H,5.30；N,7.52.P42(S,RPhos,RA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.23-8.39(m,22H),5.21(br,3H),4.57(m,1H),4.41(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4,04(m,4H),3.70(m,1H),3.36(s,1H),1.51(m,3H)；MS m/z 750,611,541,286；IR(KBr)3440,3056,2960,1645,1506,1465,1237,1127；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.59；H,5.34；N,7.51.P43(S,RPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.37(m,22H),5.22(br,3H),4.55(m,1H),4.41(m,1H),4.20(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),1.52(m,3H)；MS m/z 750,611,541,399,286；IR(KBr)3440,3056,2961,1645,1504,1465,1237,1127；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.39；H,5.45；N,7.64.P44(S,SPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.39(m,22H),5.21(br,3H),4.55(m,1H),4.40(m,1H),4.23(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.70(m,1H),3.37(s,1H),1.50(m,3H)；0MS m/z 750,611,541,286；IR(KBr)3440,3052,2960,1645,1506,1467,1127；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.88；H,5.42；N,7.38.P45(R,RPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.35(m,22H),5.23(br,3H),4.55(m,1H),4.39(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.73(m,1H),3.38(s,1H),1.50(m,3H)；MS m/z 750,611,541,399,286；IR(KBr)3440,3050,2960,1645,1500,1465,1234；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.75；H,5.43；N,7.38.P46(R,SPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.35(m,22H),5.21(br,3H),4.55(m,1H),4.41(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.05(m,4H),3.71(m,1H),3.39(s,1H),1.53(m,3H)；MS m/z 750,541,286；IR(KBr)3440,3055,2960,1645,1502,1465,1237；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.47；H,5.39；N,7.62.P47(R,RPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.21-8.36(m,22H),5.22(br,3H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.06(m,4H),3.71(m,1H),3.37(s,1H),1.51(m,3H)；MS m/z 750,541,399,286；IR(KBr)3440,3056,2960,1645,1505,1465,1238；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.49；H,5.41；N,7.63.P48(R,SPhos,SA,R=-C6H5；R’=-CH3；R”XH=聯(lián)二萘胺)；1H NMRδ7.20-8.37(m,22H),5.20(br,3H),4.57(m,1H),4.41(m,1H),4.22(m,1H),4.13(s,1H),4.07(s,1H),3.87-4.05(m,4H),3.70(m,1H),3.39(s,1H),1.53(m,3H)；MS m/z 750,611,541,399,286；IR(KBr)3441,3055,2961,1645,1506,1462,1237；元素分析C46H39N4OPFe計(jì)算值C,73.62；H,5.20；N,7.46；實(shí)測(cè)值C,73.54；H,5.19；N,7.34.P49(S,SPhos,RA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ9.25(br,1H),7.11-8.20(m,29H),5.07(t,J=1.2 Hz,1H),4.59-4.65(m,1H),4.56(t,J=1.2 Hz,1H),4.42(m,1H),4.29-4.35(m,3H),4.07(dd,J=7.2,8.1 Hz,1H),3.92(m,1H),3.74(m,2H),2.40-2.62(m,4H)；MS m/z 924,659,541,447,286；IR(KBr)3055,2967,1639,1589,1504,1461,1232,1023；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.01；H,4.90；N,3.05.P50(S,RPhos,RA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ7.11-8.20(m,29H),5.25(br,1H),5.09(t,J=1.2 Hz,1H),4.59-4.64(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.33(m,3H),4.07(dd,J=7.2,8.1 Hz,1H),3.92(m,1H),3.74(m,2H),2.41-2.62(m,4H)；MS m/z 924,659,541,286；IR(KBr)3055,2967,1640,1589,1502,1461,1023；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.18；H,4.95；N,3.09.P51(S,RPhos,SA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ9.27(br,1H),7.11-8.22(m,29H),5.11(t,J=1.2 Hz,1H),4.59-4.66(m,1H),4.59(t,J=1.2 Hz,1H),4.42(m,1H),4.29-4.35(m,3H),4.07(m,1H),3.90(m,1H),3.71(m,2H),2.41-2.63(m,4H)；MS m/z 924,541,447,286；IR(KBr)3053,2968,1639,1589,1502,1460,1232,1021；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,73.96；H,4.62；N,2.99.P52(S,SPhos,SA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ7.11-8.20(m,29H),5.23(br,1H),5.08(t,J=1.2 Hz,1H),4.59-4.64(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.33(m,3H),4.09(dd,J=7.2,8.1 Hz,1H),3.93(m,1H),3.74(m,2H),2.41-2.60(m,4H)；MS m/z 924,659,541,286；IR(KBr)3055,2969,1639,1589,1503,1461,1230；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.01；H,4.90；N,3.05.P53(R,RPhos,SA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ9.25(br,1H),7.11-8.22(m,29H),5.09(t,J=1.2 Hz,1H),4.59-4.65(m,1H),4.56(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.34(m,3H),4.07(m,1H),3.92(m,1H),3.76(m,2H),2.40-2.62(m,4H)；MS m/z 924,659,447,315,286；IR(KBr)3054,2969,1640,1589,1503,1460,1232；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.28；H,4.95；N,3.19.P54(R,SPhos,SA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ7.11-8.20(m,29H),5.25(br,1H),5.09(t,J=1.2 Hz,1H),4.59-4.63(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.33(m,3H),4.07(dd,J=7.2,8.1 Hz,1H),3.92(m,1H),3.75(m,2H),2.41-2.62(m,4H)；MS m/z 924,659,315,286；IR(KBr)3053,2968,1639,1589,1502,1461,1023；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.09；H,4.96；N,3.15.P55(R,SPhos,RA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ9.25(br,1H),7.10-8.21(m,29H),5.09(t,J=1.2 Hz,1H),4.59-4.65(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.34(m,3H),4.07(m,1H),3.91(m,1H),3.76(m,2H),2.41-2.62(m,4H)；MS m/z 924,659,541,447,315,286；IR(KBr)3055,2967,1639,1589,1503,1461,1233,1023；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.06；H,4.87；N,3.24.P56(R,RPhos,RA,R=-CH2C6H5；R’=萘基(-C10H7)；R”XH=聯(lián)二萘硫酚)1H NMRδ7.11-8.20(m,29H),5.25(br,1H),5.09(t,J=1.2 Hz,1H),4.59-4.64(m,1H),4.57(t,J=1.2 Hz,1H),4.41(m,1H),4.29-4.33(m,3H),4.08(m,1H),3.90(m,1H),3.73(m,2H),2.41-2.62(m,4H)；MS m/z 924,659,541,315；IR(KBr)3300,3052,2967,1639,1587,1504,1461,1232,1023；元素分析C57H45N2OS2PFe計(jì)算值C,74.04；H,4.87；N,3.03；實(shí)測(cè)值C,74.01；H,4.68；N,3.19.P57(S,SPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.40(m,2OH),502(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.63(m,2H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 864,611,541；IR(KBr)3321,3056,2962,1645,1506,1465,1237,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.87；H,6.54；N,3.17.P58(S,RPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.45(m,20H),5.02(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.63(m,2H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 964,611,541；R(KBr)3299,3056,2960,1643,1506,1465,1237；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.67；H,6.42；N,3.09.P59(S,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.40(m,20H),5.01(br,1H),4.55(m,1H),4.40(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.64(m,2H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=7.0 Hz,6H)；MS m/z 864,611,541,399；IR(KBr)3320,3053,2960,1643,1506,1464,1239,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.90；H,6.72；N,3.11.P60(S,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.43(m,20H),5.02(br,1H),4.55(m,1H),4.40(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.62(m,2H),2.53(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.73(t,J=7.0 Hz,6H)；MS m/z 964,611,541,399；IR(KBr)3325,3056,2961,1645,1508,1465,1237,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.62；H,6.63；N,3.44.P61(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.20-8.42(m,20H),5.00(br,1H),4.55(m,1H),4.40(m,1H),4.22(m,1H),4.14(s,1H),4.09(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.62(m,2H),2.51(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 864,611,399；IR(KBr)3360,3054,2961,1643,1506,1465,1239,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.98；H,6.62；N,3.37.P62(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.41(m,20H),5.01(br,1H),4.55(m,1H),4.42(m,1H),4.22(m,1H),4.14(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.39(s,1H),2.85(m,4H),2.65(m,2H),2.53(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=7.0 Hz,6H)；MS m/z 864,611,541；IR(KBr)3350,3054,2962,1645,1505,1465,1237,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.92；H,6.29；N,3.01.P63(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.19-8.40(m,20H),5.02(br,1H),4.55(m,1H),4.40(m,1H),4.24(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.05(m,4H),3.71(m,1H),3.38(s,1H),2.86(m,4H),2.63(m,2H),2.52(s,6H),1.82(m,1H),0.97(d,J=6.8 Hz,3H),0,91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 864,541,399；IR(KBr)3318,3054,2960,1645,1507,1465,1127；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.68；H,6.72；N,3.53.P64(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH=TADDOL 1H NMRδ7.21-8.45(m,20H),5.00(br,1H),4.53(m,1H),4.41(m,1H),4.24(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.70(m,1H),3.39(s,1H),2.84(m,4H),2.64(m,2H),2.50(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.73(t,J=7.0 Hz,6H)；MS m/z 864,611,541,399；IR(KBr)3350,3052,2963,1645,1234,1123；元素分析C51H57N2O5PFe計(jì)算值C,70.85；H,6.59；N,3.24；實(shí)測(cè)值C,70.65；H,6.44；N,3.40.P65(S,SPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.62(br,1H),4.53(m,1H),4.41(m,1H),4.18(m,1H),4.11(s,1H),4.07(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.64(m,6H),2.54(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=7.0 Hz,6H)；MS m/z 560IR(KBr)3401,3056,2963,1645,1506,1465,1237,1124；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.99；H,7.45；N,5.17.P66(S,RPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.88(br,1H),4.55(m,1H),4.44(m,1H),4.13-4.15(m,2H),4.07(s,1H),3.87-4.05(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.64(m,6H),2.52(s,6H),1.83(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.72(t,J=7.0 Hz,6H)；MS m/z 560；IR(KBr)3390,3050,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.77；H,7.49；N,5.21.P67(S,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.82(br,1H),4.52(m,1H),4.38(m,1H),4.20(m,1H),4.13(s,1H),4.09(s,1H),3.87-4.06(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.63(m,6H),2.50(s,6H),1.83(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=7.0 Hz,6H)；MS m/z 560IR(KBr)3450,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.67；H,7.49；N,5.18.P68(S,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.71(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.55-2.64(m,6H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 560,399；IR(KBr)3410,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.68；H,7.28；N,5.00.P69(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.69(br,1H),4.55(m,1H),4.40(m,1H),4.19(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.53-2.64(m,6H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=6.8 Hz,6H)；MS m/z 560,399；IR(KBr)3400,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.65；H,7.19；N,5.23.P70(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.78(br,1H),4.53(m,1H),4.40(m,1H),4.20(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.64(m,6H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=6.9 Hz,6H)；MS m/z 560,399；IR(KBr)3399,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.72；H,7.19；N,5.20.P71(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.76(br,1H),4.55(m,1H),4.40(m,1H),4.19(m,4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.66(m,6H),2.52(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=6.8 Hz,6H)；MS m/z 560,399；IR(KBr)3420,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.66；H,7.17；N,4.88.P72(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.88(br,1H),4.55(m,1H),4.43(m,1H),4.19(m,1H),4.15(s,1H),4.07(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55-2.64(m,6H),2.53(s,6H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=7.0 Hz,6H)；MS m/z 560,399；IR(KBr)3414,3056,2960,1645,1506,1465,1237,1127；元素分析C27H41N2O5PFe計(jì)算值C,57.88；H,7.32；N,5.00；實(shí)測(cè)值C,57.77；H,7.06；N,4.92.P73(S,SPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.69(br,1H),4.50(m,1H),4.41(m,1H),4.23(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.39(s,1H),2.86(t,J=7.5 Hz,4H),2.55-2.60(m,2H),2.52(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.90(d,J=6.7 Hz,3H),0.72(t,J=6.8 Hz,6H)；MS m/z 616,399；IR(KBr)3380,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.21；H,7.78；N,4.63.P74(S,RPhos,RA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.68(br,1H),4.53(m,1H),4.40(m,1H),4.24(dd,J=8.6,9.2 Hz,1H),4.14(s,1H),4.07(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.37(s,1H),2.85(m,4H),2.55-2.60(m,2H),2.51(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.90(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 616IR(KBr)3376,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.47；H,7.99；N,4.68.P75(S,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.69(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.83(d,4H),2.55-2.60(m,2H),2.52(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=6.8 Hz,6H)；MS m/z 616IR(KBr)3387,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.34；H,7.68；N,4.28.P76(S,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.65(br,1H),4.55(m,1H),4.42(m,1H),4.18(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.36(s,1H),2.85(t,J=7.5 Hz,4H),2.53-2.60(m,2H),2.52(s,6H),2.21(s,12H),1.82(m,1H),0.99(d,J=6.8 Hz,3H),0.91(d,J=6.7Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 616IR(KBr)3360,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.19；H,7.99；N,4.72.P77(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.72(br,1H),4.53(m,1H),4.41(m,1H),4.19(m,1H),4.14(s,1H),4.06(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.55-2.60(m,2H),2.52(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7Hz,3H),0.75(t,J=6.8 Hz,6H)；MS m/z 616,296；IR(KBr)3372,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.60；H,8.12；N,4.44.P78(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.77(br,1H),4.56(m,1H),4.41(m,1H),4.20(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.05(m,4H),3.73(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.55-2.62(m,2H),2.50(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7Hz,3H),0.74(t,J=7.0 Hz,6H)；MS m/z 616,296；IR(KBr)3382,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.67；H,7.89；N,4.31.P79(R,RPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.73(br,1H),4.56(m,1H),4.40(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.72(m,1H),3.37(s,1H),2.83(m,4H),2.55-2.60(m,2H),2.52(s,6H),2.21(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=6.9 Hz,6H)；MS m/z 616,296；IR(KBr)3386,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.28；H,7.95；N,4.71.P80(R,SPhos,SA,R=-C2H5；R’=-CH(CH3)2；R”XH= 1H NMRδ4.80(br,1H),4.56(m,1H),4.42(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.05(m,4H),3.73(m,1H),3.39(s,1H),2.86(d,4H),2.55-2.60(m,2H),2.52(s,6H),2.20(s,12H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=7.0 Hz,6H)；MS m/z 616,296；IR(KBr)3380,3056,2960,1645,1506,1465,1237,1127；元素分析C31H49N2O5PFe計(jì)算值C,60.41；H,7.95；N,4.55；實(shí)測(cè)值C,60.40；H,7.99；N,4.24.
實(shí)施例二
(構(gòu)型為R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)50-100℃時(shí)，471mg(1mmol)(S)-二(二乙基胺基)膦二茂鐵噁唑啉1(R=C2H5；R’=i-CH(CH3)2)，3-5mmol的1,2-反式二苯基乙二醇，溶于5-20mL苯或四氯化碳，所得的黃色溶液在80-120℃下反應(yīng)1-10小時(shí)，TLC跟蹤至反應(yīng)結(jié)束，用水洗，飽和食鹽水洗，無水硫酸鈉干燥，減壓除去溶劑，柱層析純化，得到產(chǎn)品300mg。P81(S,SPhos,RA,R=C2H5；R’=i-CH(CH3)2；R”XH=)；1H NMRδ7.21-8.21(m,10H),5.28(br,1H),4.55(m,1H),4.40(m,1H),4.22(dd,J=8.7,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.5 Hz,4H),2.56(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.75(t,J=7.0 Hz,6H)；MS m/z 612,296；IR(KBr)3300,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.82；H,6.82；N,4.68.P82(S,RPhos,RA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.21(m,10H),5.25(br,1H),4.56(m,1H),4.40(m,1H),4.22(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.07(s,1H),3.87-4.05(m,4H),3.77(m,1H),3.38(s,1H),2.85(m,4H),2.56(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.73(t,J=7.0 Hz,6H)；MS m/z 612,296；IR(KBr)3310,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.88；H,6.70；N,4.68.P83(S,RPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.21(m,10H),5.28(br,1H),4.56(m,1H),4.44(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.37(s,1H),2.83(t,J=7.5 Hz,4H),2.54(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.76(t,J=7.0 Hz,6H)；MS m/z 612,296；IR(KBr)3312,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.58；H,6.53；N,4.69.P84(S,SPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.21(m,10H),5.27(br,1H),4.57(m,1H),4.40(m,1H),4.18(dd,J=8.5,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.86(m,4H),2.56(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=6.9 Hz,6H)；MS m/z 612,296；IR(KBr)3308,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.48；H,6.82；N,4.49.P85(R,RPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.24(m,10H),5.24(br,1H),4.55(m,1H),4.40(m,1H),4.20(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.84(m,4H),2.58(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.72(t,J=7.1 Hz,6H)；MS m/z 612,296；IR(KBr)3321,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.78；H,6.71；N,4.41.P86(R,SPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.21(m,10H),5.28(br,1H),4.55(m,1H),4.41(m,1H),4.23(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.56(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.71(t,J=7.0 Hz,6H)；MS m/z 612IR(KBr)3310,3056,2960,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.84；H,6.92；N,4.68.P87(R,RPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.24(m,10H),5.25(br,1H),4.57(m,1H),4.42(m,1H),4.21(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.06(m,4H),3.70(m,1H),3.39(s,1H),2.84(t,J=7.5 Hz,4H),2.56(m,2H),1.82(m,1H),0.98(d,J=6.8 Hz,3H),0.90(d,J=6.7 Hz,3H),0.76(t,J=7.0 Hz,6H)；MS m/z 612,296；IR(KBr)3310,3056,2960,1645,1506,1465；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.56；H,6.48；N,4.49.P88(R,SPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=1,2-反式二苯基乙二醇)；1H NMRδ7.21-8.21(m,10H),5.28(br,1H),4.56(m,1H),4.40(m,1H),4.22(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.72(m,1H),3.39(s,1H),2.87(m,4H),2.56(m,2H),1.81(m,1H),0.98(d,J=6.8 Hz,3H),0.91(d,J=6.7 Hz,3H),0.74(t,J=6.8 Hz,6H)；MS m/z 612,296；IR(KBr)3310,3056,2964,1645,1506,1465,1237,1127；元素分析C34H41N2O3PFe計(jì)算值C,66.69；H,6.70；N,4.57；實(shí)測(cè)值C,66.71；H,6.58；N,4.62.P89(S,SPhos,RA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.77(br,1H),4.52(m,1H),4.40(m,1H),4.17(dd,J=8.0,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.7 Hz,4H),2.56(m,2H),1.82(m,1H),0.42-1.62(m,21H)；MS m/z 542,296；IR(KBr)3320,3050,2968,1640,1501,1467,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.14；H,7.82；N,4.98.P90(S,RPhos,RA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.79(br,1H),4.50(m,1H),4.47(m,1H),4.15(m,1H),4.13(s,1H),4.10(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.7 Hz,4H),2.56(m,2H),1.82(m,1H),0.40-1.65(m,21H)；MS m/z 542,296；IR(KBr)3318,3049,2968,1641,1501,1467,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.25；H,7.99；N,5.12.P91(S,RPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.77(br,1H),4.52(m,1H),4.40(m,1H),4.17(dd,J=8.0,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.7 Hz,4H),2.56(m,2H),1.82(m,1H),0.42-1.62(m,21H)；MS m/z 542,296；IR(KBr)3320,3050,2968,1640,1501,1467,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.21；H,7.77；N,4.86.P92(S,SPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.82(br,1H),4.55(m,1H),4.40(m,1H),4.18(dd,J=8.2,9.2 Hz,1H),4.14(s,1H),4.08(s,1H),3.87-4.06(m,4H),3.71(m,1H),3.38(s,1H),2.85(t,J=7.7 Hz,4H),2.58(m,2H),1.83(m,1H),0.42-1.65(m,21H)；MS m/z 542,296；IR(KBr)3326,3050,2968,1640,1505,1467,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.02；H,7.99；N,5.05P93(R,RPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.82(br,1H),4.52(m,1H),4.40(m,1H),4.17(m,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.38(s,1H),2.85(m,4H),2.55(m,2H),1.82(m,1H),0.40-1.62(m,21H)；MS m/z 542,296；IR(KBr)3318,3050,2967,1640,1501,1467,1125；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N5.16；實(shí)測(cè)值C,61.88；H,7.79；N,4.92P94(R,SPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.72(br,1H),4.52(m,1H),4.40(m,1H),4.17(dd,J=8.0,9.3 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.72(m,1H),3.38(s,1H),2.87(t,J=7.8 Hz,4H),2.55(m,2H),1.82(m,1H),0.42-1.66(m,21H)；MS m/z 542,296；IR(KBr)3310,3050,2968,1640,1501,1467,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,61.97；H,8.10；N,4.94P95(R,RPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.77(br,1H),4.52(m,1H),4.40(m,1H),4.17(dd,J=8.0,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.87-4.04(m,4H),3.71(m,1H),3.35(s,1H),2.89(m,4H),2.55(m,2H),1.84(m,1H),0.40-1.62(m,21H)；MS m/z 542,296；IR(KBr)3308,3050,2968,1644,1501,1463,1123；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.18；H,7.82；N,4.93P96(R,SPhos,SA,R=-CH(CH3)2；R’=-CH(CH3)2；R”XH=1,2-反式環(huán)己二醇)；1H NMRδ4.79(br,1H),4.54(m,1H),4.41(m,1H),4.17(dd,J=8.0,9.2 Hz,1H),4.13(s,1H),4.08(s,1H),3.86-4.04(m,4H),3.73(m,1H),3.39(s,1H),2.89(m,4H),2.56(m,2H),1.82(m,1H),0.42-1.65(m,21H)；MS m/z 542,296；IR(KBr)3320,3051,2968,1637,1501,1466,1121；元素分析C28H43N2O3PFe計(jì)算值C,62.01；H,7.93；N,5.16；實(shí)測(cè)值C,62.29；H,7.93；N,5.11實(shí)施例三[Pd(C3H5)Cl]23.7mg(0.01mmol)和配體P3(A,RPhos,SA,R=C2H5；R’=i-CH(CH3)2；R”XH=聯(lián)二萘酚)(實(shí)例一中合成的配體)13mg(0.02mmol)于4mL四氫呋喃中絡(luò)合0.5-10小時(shí),加入1,3-二苯基烯丙基醋酸酯252mg(1mmol),芐胺214mg(1mmol),然后于室溫反應(yīng)，TLC跟蹤至反應(yīng)結(jié)束，用乙醚提取，飽和食鹽水洗，無水硫酸鈉干燥，減壓除去溶劑，柱層析純化，得到N-芐基-1,3-二苯基烯丙基胺無色液體295mg(99％yield；95％ee)；1HNMR(300 MHz,CDCl3)δ1.76(s,1H),3.77(s,2H),4.39(d,J=7.4 Hz,1H),6.31(dd,J=7.4,15.6 Hz,1H),6.58(d,J=15.6 Hz,1H),7.10-7.5 3(m,15H)；MS m/z 299(M+).
實(shí)施例四[Pd(C3H5)Cl]23.7mg(0.01mmol)和配體P25(S,SPhos,SA,R=C2H5；R’=-CH2C6H5；R”XH=聯(lián)二萘酚)(實(shí)例一中合成的配體)15mg(0.02mmol)于4mL二氯甲烷中絡(luò)合0.5-10小時(shí)，加入1-萘基烯丙基醋酸酯226mg(1mmol)，丙二酸二甲酯(0.34mL，3mmol)，N,O-二(三甲硅基)乙酰胺(0.74mL，3mmol)，然后于室溫反應(yīng)，TLC跟蹤至反應(yīng)結(jié)束，用乙醚提取，飽和食鹽水洗，無水硫酸鈉干燥，減壓除去溶劑，柱層析純化，得到3-(1-萘基)-1-丁烯-4,4-二甲酸甲酯無色液體295mg(99％yield；97％ee)；1HNMR(300MHz,CDCl3)δ3.99(s,3H),3.79(s,3H),4.17(d,J=10.9 Hz,1H),5.04(dd,J=8.1,10.9 Hz,1H),5.11(d,J=10.2 Hz,1H),5.17(d,J=17.1 Hz,1H),6.09(m,1H),7.47-8.25(m,7H).
權(quán)利要求
1．一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式為 其中R=苯基、萘基或1-8個(gè)碳的烷基，R′=苯基、萘基或1-8個(gè)碳的烷基，R″=5-32個(gè)碳的烷基或芳基，X=NH、O或S。
2．如權(quán)利要求1所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式為 其中R、R′、R″、X如權(quán)利要求1所述。
3．如權(quán)利要求1所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式為 其中R、R′、R″、X如權(quán)利要求1所述。
4．如權(quán)利要求1所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式為 其中R、R′、R″、X如權(quán)利要求1所述。
5．如權(quán)利要求1所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體，其分子通式為 其中R、R′、R″、X如權(quán)利要求1所述。
6．如權(quán)利要求1所述一種具有多種手性中心的二茂鐵噁唑啉膦配體的合成方法，其特征是取代的二茂鐵-4-取代的噁唑啉具有分子通式是 式中R、R′如權(quán)利要求1所述，所述的手性化合物HXR″XH=5-32個(gè)碳的手性二醇、手性二胺、手性二酚、手性二硫醇或手性二硫酚，式中R″、X如權(quán)利要求1所述。
7．如權(quán)利要求6所述一種具有多種手性中心的二茂鐵噁唑啉膦配體的合成方法，其特征是所述的有機(jī)溶劑是包括苯、四氯化碳、四氫呋喃、乙醚、二氯甲烷、甲苯、環(huán)己烷、石油醚、丙酮、吡啶、CHCl3、正己烷、正庚烷、二氧六環(huán)在內(nèi)的極性或非極性溶劑。
8．如權(quán)利要求6所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體的合成方法，其特征是所述的氮原子上含有孤對(duì)電子的有機(jī)胺化合物是四甲基二乙胺、聯(lián)二吡啶、三辛胺、對(duì)二甲胺基吡啶，三乙胺，二異丙基乙基胺。
9．如權(quán)利要求6所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體的合成方法，其特征是反應(yīng)產(chǎn)物用柱層析或重結(jié)晶的方法拆分。
10．如權(quán)利要求1所述的一種具有多種手性中心的二茂鐵噁唑啉膦配體的用途，其特征是用作制備具有手性的烯丙基羧酸或氨基衍生物。
全文摘要
本發(fā)明是一種具有多種手性中心的二茂鐵噁唑啉膦配體、合成及用途,該配體中含有噁唑啉、膦原子的中心手性和取代反應(yīng)物的軸或中心手性等,其由二(二胺基)膦取代的二茂鐵噁唑啉與手性的二醇、二胺、二酚、二硫醇或二硫酚經(jīng)催化反應(yīng)制得。再生的一個(gè)手性的膦通?？捎弥鶎游龌蛑亟Y(jié)晶分開。該類配體在烯丙基取代反應(yīng)中對(duì)映選擇性好,尤其對(duì)單取代的反應(yīng)底物區(qū)域選擇性好,在氫化,硅氫化等不對(duì)稱催化反應(yīng)中亦有較好的應(yīng)用前景。
文檔編號(hào)C07C51/00GK1299820SQ00127948
公開日2001年6月20日 申請(qǐng)日期2000年12月19日 優(yōu)先權(quán)日2000年12月19日
發(fā)明者游書力, 侯雪龍, 戴立信 申請(qǐng)人:中國(guó)科學(xué)院上海有機(jī)化學(xué)研究所