CN110002980B - 一种钯催化不对称萘基化的方法及其在合成轴手性联芳基醛类催化剂中的应用 - Google Patents
一种钯催化不对称萘基化的方法及其在合成轴手性联芳基醛类催化剂中的应用 Download PDFInfo
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Abstract
本发明公开了一种以钯催化不对称萘基化为关键反应合成轴手性联芳基醛类催化剂的方法,此方法的特点通过钯催化萘基化得到轴手性联芳化合物,该化合物通过羟基化、亲电溴代合成轴手性联芳基醛催化剂。其中,钯催化不对称萘基化反应是以2‑醛基联芳类化合物为原料,1,4‑环氧‑1,4‑二氢萘为萘基来源在原料的轴邻位不对称引入萘基选择性合成轴手性联芳醛类化合物。本发明能够高效合成多种轴手性萘基化联芳基醛化合物,通过连续三步碳氢键官能团化能够合成具有高活性、高选择性的手性醛配体,该配体在应用中展现出了较高的手性诱导。
Description
技术领域
本发明涉及一种钯催化不对称萘基化的方法及其在合成轴手性联芳基醛类催化剂中的应用,属于导向的过渡金属催化的不对称碳氢键活化领域。
背景技术
在有机合成中,醛是一类重要的合成子。值得一提的是,醛类化合物能够作为催化剂用于醛催化之中。特别地,近年来对于手性醛催化剂的合成与应用备受关注。醛类催化剂由最初的含有吡哆醛类结构的缩合酶发展到吡哆醛类小分子化合物。与此同时,手性甘油醛也有报道用于手性分子的合成之中。这些催化剂普遍存在以下问题,如较局限的反应范围,较差的手性诱导等。轴手性联芳结构广泛存在于天然产物和药物之中。特别的是,在不对称合成中,常用的手性催化剂如联萘芳结构的手性二醇、手性磷酸都具有轴手性联芳结构。轴手性结构的醛是一类新型配体,能够应用于活化氨类化合物的邻位,其对有机催化模式的发展有着重要的意义。因此发展新的方法来合成全新的轴手性联芳基醛结构就显得尤为重要。
最近,轴手性联芳基醛类催化剂的合成及其应用取得了突破性的进展。2014年,郭其祥课题组报道了一例手性联萘酚衍生的醛催化剂,实现了2-氨基丙二酸与3-吲哚甲烷的对映选择性α-烷基化(B.Xu,L.-L.Shi, Y.-Z.Zhang,Z.-J.Wu,L.-N.Fud,C.-Q.Luo,L.-X.Zhang,Y.-G.Peng,Q.-X. Guo,Chem.Sci.2014,5,1988.)。基于以上研究,该课题组对手性联萘酚进一步改造,所得的新型配体能够实现甘氨酸酯的不对称活化(W.Wen,L. Chen,M.-J.Luo,Y.Zhang,Y.-C.Chen,Q.Ouyang,Q.-X.Guo,J.Am.Chem. Soc.2018,140,9774)。值得一提的是,赵宝国课题组发展了一类N-季铵联芳轴手性吡哆醛结构的催化剂,该催化剂能够实现甘氨酸的不对称曼尼期反应(J.Chen,X.Gong,J.Li,Y.Li,J.Ma,C.Hou,G.Zhao,W.Yuan,B.Zhao, Science,2018,360,1438.)。尽管这些轴手性联芳醛开创性的实现了几例不对称转化,但也存在一定的问题,如有限的底物范围,较低的立体控制及催化效率、合成步骤繁琐等。为了快速、高效构建轴手性联芳基醛配体,我们发展了氨基酸作为瞬态导向基钯催化不对称萘基化的方法,通过萘基化、羟基化、亲电溴代连续三步碳氢键官能团化合成了一系列轴手性联芳醛催化剂,其对有机小分子催化及手性配体类型的发展等都有重要意义。
发明内容
本发明的目的是提供一种以钯催化不对称萘基化反应以及以该反应为关键步骤合成轴手性联芳基醛催化剂的高效合成方法。该合成轴手性联芳基醛催化剂的路线反应条件温和、操作简便、合成步骤较短,能够高效的合成高立体选择性的轴手性联芳基醛催化剂。
一种钯催化不对称萘基化的方法,包括:
在钯催化剂、手性助剂和添加剂的作用下,联芳基醛与1,4-桥氧二氢萘发生不对称萘基化反应,反应结束后经过后处理得到轴手性联芳化合物;
所述的添加剂由酸和碱组成;
反应式如下:
其中,R1-R4、R5-R8独立地选自H、烷基、烷氧基、卤素、三氟甲基或酯基,或者R1、R2与同它们相连的苯环共同形成萘基,或者R5、R6与同它们相连的苯环共同形成萘基;
R’独立地选择H、烷基、烷氧基、卤素或羟基中的一个或者多个。
本发明在反应过程中通过氨基酸手性控制,可以使得萘基化产物具有 90%~>99%ee值。
作为优选,R1-R4、R5-R8独立地选自H、甲基、乙基、叔丁基、三氟甲基、氟、氯、甲氧基、酯基中的一个或者多个;
R’独立地选自H、甲基、甲氧基、F、Cl、Br和羟基中的一个或者多个,进一步优选为H。
作为优选,所述的钯催化剂为醋酸钯或三氟醋酸钯,进一步优选为醋酸钯。
作为优选,所述的手性助剂为手性纯的氨基酸,优选为L-叔亮氨酸。
作为优选,所述的酸为苯甲酸、特戊酸、金刚烷甲酸或金刚烷乙酸;进一步优选为金刚烷乙酸;
所述的碱为乙醇钠、醋酸钠、三氟乙酸钠、氟化钠、磷酸氢二钠、苯甲酸钠或正丁酸钠;进一步优选为正丁酸钠。
作为优选,反应在有机溶剂中进行,所述的有机溶剂为三氟乙醇、醋酸、六氟异丙醇中的一种或者多种;进一步优选为三氟乙醇和醋酸的混合溶剂,体积比为9:1。
作为优选,反应温度为50~70℃,反应时间为24~48小时。
作为优选,联芳基醛、1,4-环氧-1,4-二氢萘、钯催化剂、酸、碱、手性助剂的摩尔比为1:1.5:0.1:2:2.5:0.3。
本发明还提供了一种所述的方法在合成轴手性联芳基醛类催化剂中的应用,包括以下步骤:
(1)按照上述的方法得到轴手性联芳化合物;
(2)步骤(1)得到的轴手性联芳化合物进行羟基化反应,得到羟基化产物;
(3)步骤(2)得到的羟基化产物进行亲电溴代,得到所述的轴手性联芳基醛类催化剂;
反应式如下:
R1,R2独立地选自H、烷基、芳基或卤素。
步骤(2)中,所述的羟基化反应在醋酸钯的催化下,2-氨基-4-氯苯甲酸、对甲苯磺酸一水合物和1-氟-2,4,6-三甲基吡啶三氟甲烷磺酸盐的存在下,于醋酸溶剂中进行;
步骤(3)中,所述的溴代试剂为N-溴代丁二酰亚胺,反应在二氯甲烷中进行。
其中,步骤(2)中,以轴手性联芳化合物为基准,其他物质的用量如下:2-氨基-4-氯苯甲酸0.5当量,醋酸钯0.2当量,对甲苯磺酸一水合物 2.0当量,1-氟-2,4,6-三甲基吡啶三氟甲烷磺酸盐1.5当量,醋酸(1.0M,即加入量使底物轴手性联芳化合物为0.1M);
步骤(3)中,亲电溴代的反应条件如下:N-溴代丁二酰亚胺2.5-5.0 当量,二氯甲烷作为溶剂,反应温度为室温到45℃。
本发明的后处理方式优选为薄层硅胶板层析。
同现有技术相比,本发明的有益效果体现在:
(1)反应底物适用性广。
(2)反应立体选择性强,通过氨基酸手性控制,可以使产物具有很高的ee值。
(3)合成轴手性联芳基醛催化剂的步骤短,合成效率高,在不对称活化甘氨酸酯的过程中,体现出很高的活性,能够诱导出较高的ee。
附图说明
图1为实施例1得到的化合物1以及其消旋体的HPLC图谱,其中, HPLC图谱的条件为AD-H,n-hexane/2-propanol=90/10,v=0.7mL·min-1, λ=220nm。
图2为化合物27以及其消旋体的HPLC图谱。其中,HPLC图谱的条件为AS-H,n-hexane/2-propanol=95/5,v=0.5mL·min-1,λ=254nm。
图3为化合物32以及其消旋体的HPLC图谱。其中,HPLC图谱的条件为AD-H,n-hexane/2-propanol=90/10,v=0.8mL·min-1,λ=254nm。
具体实施方式
以下结合具体实施例解释本发明,而不是对本发明进行限制。
实施例1
在反应器中,加入0.1毫摩尔2-萘基苯甲醛、0.15毫摩尔1,4-环氧-1,4- 二氢萘、0.01毫摩尔醋酸钯催化剂、0.25毫摩尔金刚烷乙酸、0.03毫摩尔L-叔亮氨酸、0.2毫摩尔正丁酸钠和1毫升溶剂(三氟乙醇:醋酸=0.9: 0.1),在60℃空气气氛中反应48小时后结束反应进行后处理,通过薄层硅胶板层析得到结构如式1的产物1,产率为71%,ee值为>99%。化合物1以及其消旋体的HPLC图谱见图1。
产物1结构如下:
结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.67(s,1H),8.05(d,J=8.5Hz,1H),7.99 (d,J=8.1Hz,1H),7.89(d,J=7.7Hz,1H),7.76–7.66(m,3H),7.64–7.51 (m,4H),7.47–7.36(m,6H),7.18(dd,J=8.5,1.8Hz,1H);13C NMR(101 MHz,CDCl3)δ191.80,143.02,139.67,138.80,135.07,133.55,133.30, 133.18,133.08,132.79,132.06,129.06,128.88,128.31,128.16,128.11, 127.80,127.67,127.56,127.39,127.16,126.53,126.30,126.29,126.18. HRMS(EI-TOF)calcd for C27H18O(M+):358.1352,found:358.1357;IR (neat):ν30142897,1697,1508,1268,1216,1094cm-1
化合物1ee值的测定:HPLC with a Daicel Chiralpak AD-H, n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=220nm,t(minor)=16.6 min,t(major)=11.2min,>99%ee;[α]D 20=-42.2(c=1.00,CHCl3).
实施例2~26
操作步骤同实施例1,区别在于:改变原料芳环上的取代基或改变1,4- 环氧-1,4-二氢萘上取代基,则可以得到不同轴手性萘基化联芳产物(见表 1)。
表1实施例2~26合成轴手性联芳的实验结果
实施例27
在100mL反应器中,加入2.0毫摩尔2-([2,2'-联萘]-1-基)苯甲醛、1.0 毫尔2-氨基4-氯苯甲酸、0.4毫摩尔醋酸钯催化剂、3.0毫摩尔1-氟-2,4, 6-三甲基吡啶三氟甲磺酸盐、4.0毫摩尔对甲苯磺酸一水和物、20毫升醋酸,在90℃氮气气氛中反应18小时后结束反应进行后处理,通过薄层硅胶板层析得到产物27,产率为41%,ee值为99%。化合物27以及其消旋体的HPLC图谱见图2。
产物表征数据如下:
1H NMR(400MHz,CDCl3)δ11.55(s,1H),9.47(s,1H),8.03(d,J=8.3 Hz,1H),7.97(d,J=8.1Hz,1H),7.74(ddd,J=18.4,6.4,3.4Hz,2H),7.69– 7.61(m,3H),7.57–7.41(m,6H),7.21(d,J=8.5Hz,1H),6.95–6.81(m, 2H).13C NMR(101MHz,CDCl3)δ196.70,162.74,144.19,139.67,138.72, 136.41,133.27,133.21,132.77,132.55,132.19,129.05,128.81,128.28, 128.27,128.13,127.73,127.49,127.26,126.58,126.40,126.30,124.15, 119.29,117.39.HRMS(ESI-TOF)calcd for C27H18O2(M+Na+):397.1199, found:397.1197;IR(neat):ν2973,2915,1649,1501,1449,1379,1313,1269, 1195,1066cm-1;
化合物27ee值的测定:HPLC with a Daicel Chiralpak AS-H, n-hexane/2-propanol=95/5,v=0.5mL·min-1,λ=254nm,t(minor)=14.4 min,t(major)=15.4min,99%ee;[α]D 20=-119.0(c=0.5,CHCl3).
实施例28~31
28~31操作步骤同实施例27,区别在于:改变原料芳环上的取代基,则可以得到不同羟基化联芳产物(见表2)。
实施例32
在100mL反应器中,加入0.5毫摩尔2-([2,2'-联萘]-1-基)-6-羟基苯甲醛、2.5毫尔溴代丁二酰亚胺、5毫升二氯甲烷,反应过夜后,结束反应进行后处理,通过薄层硅胶板层析得到产物32,产率为91%,ee值为>99%;化合物32以及其消旋体的HPLC图谱见图3。
化合物32ee值的测定:HPLC with a Daicel Chiralpak AD-H, n-hexane/2-propanol=90/10,v=0.8mL·min-1,λ=254nm,t(minor)=8.3 min,t(major)=10.8min,>99%ee;
实施例33~36
33~36操作步骤同实施例32,区别在于:改变原料芳环上的取代基,则可以得到不同溴代联芳产物(见表2)。
表2实施例27~36合成轴手性联芳基醛催化剂的实验结果
[a]反应条件:1)rac-1(1.0eq.),7-oxabenzonorbornadiene(1.5eq.), Pd(OAc)2(0.1eq.),L1(0.3eq.),AdCH2CO2H(2.5eq.),nPrCO2Na(2.0eq.), TFE/HOAc=9:1(1.0M),60℃,air,48h;
2)3(1.0eq.),2-amino-4-chlorobenzoic acid(0.5eq.),Pd(OAc)2(0.2eq.),TsOH·H2O(2.0eq.),1-fluoro-2,4,6-trimethylpyridnium triflate(1.5eq.), HOAc(1.0M),90℃,16h;
3)NBS(2.5–5.0eq.),DCM。
Claims (8)
2.根据权利要求1所述的钯催化不对称萘基化的方法,其特征在于,
R1-R4、R5-R8独立地选自H、甲基、乙基、叔丁基、三氟甲基、氟、氯、甲氧基、酯基中的一个;
R’独立地选自H、甲基、甲氧基、F、Cl、Br和羟基中的一个。
3.根据权利要求1所述的钯催化不对称萘基化的方法,其特征在于,所述的钯催化剂为醋酸钯或三氟醋酸钯。
4.根据权利要求1所述的钯催化不对称萘基化的方法,其特征在于,反应在有机溶剂中进行,所述的有机溶剂为三氟乙醇、醋酸、六氟异丙醇中的一种或者多种。
5.根据权利要求1所述的钯催化不对称萘基化的方法,其特征在于,反应温度为50~70oC,反应时间为24~48小时。
6.根据权利要求1所述的钯催化不对称萘基化的方法,其特征在于,联芳、1,4-环氧-1,4-二氢萘、钯催化剂、酸、碱、手性助剂的摩尔比为1 :1.5 :0.1 :2 : 2.5 :0.3。
8.根据权利要求7所述的应用,其特征在于, 步骤(3)中,所述的溴代试剂为N-溴代丁二酰亚胺,反应在二氯甲烷中进行。
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