CN106496155B - 一种氨基噻唑啉手性配体及其制备方法和应用 - Google Patents

一种氨基噻唑啉手性配体及其制备方法和应用 Download PDF

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CN106496155B
CN106496155B CN201610932167.0A CN201610932167A CN106496155B CN 106496155 B CN106496155 B CN 106496155B CN 201610932167 A CN201610932167 A CN 201610932167A CN 106496155 B CN106496155 B CN 106496155B
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aminothiazole
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傅滨
麻红利
白慧
谢磊
张振华
覃兆海
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Abstract

本发明公开了一种苯环为骨架的氨基噻唑啉手性配体化合物及其制备方法和应用。以邻硝基苯甲酸为原料，手性氨基醇为手性源，经三步“一锅法”非常简便地合成含苯环骨架结构的氨基噻唑啉手性配体。该手性配体化合物制成的Pd(II)络合物在催化丙二酸酯和(E)‑1,3‑二苯基‑2‑烯丙基乙酸酯的不对称烯丙基烷基化反应中表现出优异的对映选择性，为有机合成领域提供了一种新型手性配体化合物或催化剂。本发明氨基噻唑啉配体化合物的结构式通式如下：

Description

一种氨基噻唑啉手性配体及其制备方法和应用
技术领域
本发明属于有机合成技术领域，涉及一种氨基噻唑啉手性配体化合物及其制备方法和应用，具体涉及一种含苯环骨架结构的氨基噻唑啉手性配体化合物及其制备方法和在不对称烯丙基烷基化反应中的应用。
背景技术
在过去几十年里，不对称催化领域取得了迅猛发展，最为显著的是开发了多种具有优异催化特性的手性配体。手性配体的开发是不对称催化领域永恒的主题。目前，手性噻唑啉配体是一种尚未被完全开发的手性配体，根据噻唑啉环的数目可以分为单噻唑啉、双噻唑啉和三噻唑啉配体等三类。有关噻唑啉配体的合成及其在不对称合成中应用的文献报道较少。多数研究是结合与噁唑膦配体催化性能的比较来进行的。值得注意的是，2014年杜大明课题组[Peng,J.-H.;Du,D.-M.RSC Adv.2014,4,2061]研究发现在β-酮酸酯和β-酰胺的不对称氟化反应中，手性双噻唑啉配体-Cu(OTf)2络合物比相应的噁唑啉配体-Cu(OTf)2络合物给出更高的对映选择性。也说明手性噻唑啉配体是一类具有很大开发潜力的手性配体，其不能被认为仅仅是噁唑啉配体的类似物。本课题组[Liu,L.et al.TetrahedronAsymmetry,2012,22,550]开发的芳甲叉双噻唑啉配体在催化吲哚与苯甲叉丙二酸酯的Friedel-Crafts烷基化反应中表现出优异的催化效果（99%yield，99%ee）。因此开发全新的基于手性噻唑啉环的配体具有重要的理论和实际应用价值。
发明内容
本发明的目的是提供一种新的氨基噻唑啉手性配体化合物。以廉价的邻硝基苯甲酸为原料，手性氨基醇为手性源，非常简洁的合成一种全新的含苯环骨架结构的氨基噻唑啉手性配体化合物。本发明提供的氨基噻唑啉配体化合物的结构通式如下：
式I中：
R1选自氢，烷基，芳基，卤素，硝基，氰基；
R2和R3分别选自氢，烷基，芳基，卤素，-CO2R4或-C(R5)2OR6，所述R4选自烷基或环烷基，芳基；R5选自氢，烷基或环烷基，芳基；R6选自氢，烷基，芳基，三甲基硅基，叔丁基二甲基硅基。
噻唑啉环上4位或5位为手性碳原子。
进一步，所述氨基噻唑啉手性配体化合物是如下I-a～I-e中的一种：
I-a：R1=H,R2=Ph,R3=H,手性碳构型：S
I-b：R1=H,R2=Bn,R3=H,手性碳构型：S
I-c：R1=H,R2=-CH(CH3)2,R3=H,手性碳构型：S
I-d：R1=H,R2=-CHCH2(CH3)2,R3=H,手性碳构型：S
I-e：R1=H,R2=-CH3,R3=H,手性碳构型：S
本发明的另一个目的是提供一种氨基噻唑啉手性配体化合物的制备方法，以邻硝基苯甲酸为原料，依次历经三个步骤，“一锅法”合成。反应式及步骤如下：
（1）酰化：将邻硝基苯甲酸或邻氨基苯甲酸和酰化试剂二氯亚砜、草酰氯、五氯化磷或三氯氧磷按摩尔比1:(1.2～20)在0～100℃反应0.5～24h，即得到相应的酰氯中间体；
（2）酰胺化：将步骤（1）得到的酰氯中间体和相应的手性氨基醇按摩尔比1:(1.2～5)加入到惰性有机溶剂四氢呋喃、二氯甲烷或氯仿中，在过量的有机碱：吡啶、三乙胺、DBU；或无机碱：NaOH，NaHCO3存在下，于室温～-78℃搅拌反应0.5～24h，即生成羟基酰胺II；
（3）环化/还原：将步骤（2）得到的羟基酰胺II和五硫化二磷按摩尔比1:(2～20)加入到惰性溶剂甲苯或苯中，在有机碱吡啶或三乙胺的存在下，80～120℃搅拌反应2～48h，即生成相应的氨基噻唑啉化合物。
进一步，上述步骤（1）中邻硝基苯甲酸（或邻氨基苯甲酸）是市售的。
进一步，上述步骤（2）中手性氨基醇是L和D两种构型，由天然或非天然的氨基酸制得。
进一步，上述步骤（2）中惰性有机溶剂四氢呋喃、二氯甲烷或氯仿的用量是手性氨基醇摩尔量的20～200倍。
进一步，所述步骤（3）的反应中分子内脱水关环的同时，硝基被还原成氨基。
进一步，上述步骤（3）中，惰性溶剂苯或甲苯的用量是羟基酰胺II摩尔量的40～100倍。有机碱吡啶或三乙胺的用量是羟基酰胺II摩尔量的4～30倍。
本发明的又一个目的是提供一种氨基噻唑啉手性配体化合物与金属盐制成的Pd(II)或Pd(0)络合物，用于催化如下不对称烯丙基烷基化反应的应用，
本发明的优点：
本发明氨基噻唑啉配体化合物制备方法工艺简便，原料价廉易得，避免了邻氨基苯甲酸（属于国家管控化学品，很难购买到）作为起始原料。反应条件温和，易于操作。所得氨基噻唑啉配体化合物结构新颖，可以与过渡金属形成络合物手性催化剂，表现出良好的不对称催化性能，在催化丙二酸酯和(E)-1,3-二苯基-2-烯丙基乙酸酯的不对称烯丙基烷基化反应中表现出优异的对映选择性，为有机合成领域提供了一种新型手性配体化合物或催化剂，为发展新的不对称合成方法学提供了有力的实验基础，为发展新医药和新农药及新材料提供有力的合成工具。
具体实施方式
以下结合实施例对本发明作进一步说明。以下的实施例是本发明的进一步说明，而不是以任何方式限制本发明。本领域的技术人员根据发明的上述内容的一些非本质的改进和调整均属于本发明的保护范围。
实施例1配体2-[(S)-4,5-二氢化-4-苯基-2-噻唑啉基]苯胺I-a的合成
于50mL圆底烧瓶中加入邻硝基苯甲酸0.5g(3.0mmol),二氯亚砜0.5mL，加热回流4h，冷却至室温，减压旋蒸除去过量的二氯亚砜，得相应的酰氯中间体，并用干燥的二氯甲烷10mL溶解。于另一反应瓶中加入L-苯甘氨醇0.49g(3.6mmol)，二氯甲烷30mL和三乙胺5mL，体系降温至0℃。将上步所得酰氯的二氯甲烷溶液加入其中。完毕，室温搅拌4h。减压旋蒸除去溶剂，得相应的羟基酰胺中间体，不再进一步纯化直接用于下一步反应。
加入30mL甲苯和5mL三乙胺，加热至回流状态，分三批共加入五硫化二磷2.66g(12mmol)，加料完毕，继续回流4h，反应完毕。冷却至室温，倾出反应液，乙酸乙酯洗涤反应瓶，并与倾出液合并，减压旋蒸脱去溶剂后得粗产品，直接通过硅胶层析柱分离提纯（乙酸乙酯/石油醚=1:3，v/v），得到目标产物I-a：黄色固体,62%收率；m.p.52～54℃， 1H NMR(300MHz,CDCl3)δ7.60(dd,J=8.1,1.4Hz,1H),7.54–7.31(m,5H),7.30–7.22(m,1H),6.80–6.68(m,2H),6.32(s,2H),5.82(t,J=9.0Hz,1H),3.73(dd,J=10.9,8.5Hz,1H),3.21(dd,J=10.8,9.5Hz,1H).13C NMR(75MHz,CDCl3)δ169.35,147.55,142.13,132.15,131.46,128.35,127.29,126.21,115.88,115.71,114.39,80.57,39.01.
高分辨质谱数据：ESI-HRMS Calcd for C15H15N2S[M+H]+:255.0950,Found:255.0954.
实施例2配体2-[(S)-4,5-二氢化-4-苄基-2-噻唑啉基]苯胺I-b的合成
以L-苯丙氨醇代替实例1中的L-苯甘氨醇，其余同实施例1，得到氨基噻唑啉配体I-b，黄色固体，产率53%，m.p.70～72℃， 其核磁质谱数据如下：
1H NMR(300MHz,CDCl3)δ7.54(dd,J=8.1,1.3Hz,1H),7.45–7.17(m,6H),6.86–6.63(m,2H),6.25(s,2H),5.09–4.91(m,1H),3.29(ddd,J=18.3,12.2,7.3Hz,2H),3.08(dd,J=10.9,7.4Hz,1H),2.97(dd,J=13.5,7.9Hz,1H).13C NMR(75MHz,CDCl3)δ167.78,147.39,138.68,132.03,131.25,128.97,128.18,126.12,115.86,115.64,114.50,78.79,40.80,35.50.
高分辨质谱数据：ESI-HRMS Calcd for C16H17N2S[M+H]+:269.1107,Found:269.1107.
实施例3配体2-[(S)-4,5-二氢化-4-异丙基-2-噻唑啉基]苯胺I-c的合成
以L-缬氨醇代替实例1中的L-苯甘氨醇，其余同实施例1，得到氨基噻唑啉配体I-c，黄色油，产率49%，其核磁质谱数据如下：
1H NMR(300MHz,CDCl3)δ7.45(dd,J=7.8,1.4Hz,1H),7.17(ddd,J=8.5,7.2,1.5Hz,1H),6.75–6.60(m,2H),6.25(s,2H),4.44(ddd,J=9.7,8.4,6.8Hz,1H),3.29(dd,J=10.8,8.4Hz,1H),2.99(dd,J=10.7,9.8Hz,1H),2.12–1.92(m,1H),1.12(d,J=6.7Hz,3H),1.04(d,J=6.7Hz,3H).13C NMR(75MHz,CDCl3)δ166.96,147.29,131.91,131.02,115.83,115.57,114.69,84.22,33.72,33.14,19.63,19.19.
高分辨质谱数据：ESI-HRMS Calcd for C12H17N2S[M+H]+:221.1107,Found:221.1111.
实施例4配体2-[(S)-4,5-二氢化-4-异丁基-2-噻唑啉基]苯胺I-d的合成
以L-亮氨醇代替实例1中的L-苯甘氨醇，其余同实施例1，得到氨基噻唑啉配体I-d，黄色油，产率50%，其核磁质谱数据如下：1H NMR(300MHz,DMSO)δ7.59–7.49(m,1H),7.23(ddd,J=8.6,7.3,1.5Hz,1H),6.73(dtd,J=8.2,3.5,1.1Hz,2H),6.31(br s,2H),4.89–4.70(m,1H),3.40(dd,J=10.7,8.0Hz,1H),2.94(dd,J=10.7,8.4Hz,1H),2.02–1.79(m,2H),1.55(dt,J=13.5,6.9Hz,1H),1.10(d,J=6.5Hz,3H),1.07(d,J=6.5Hz,3H).13C NMR(75MHz,CDCl3)δ167.17,147.61,132.29,131.37,116.15,115.92,114.97,76.20,44.70,36.87,26.24,22.96,22.61.
高分辨质谱数据：ESI-HRMS Calcd for C13H19N2S[M+H]+:235.1263,Found:234.1265
实施例5配体2-[(S)-4,5-二氢化-4-甲基-2-噻唑啉基]苯胺I-e的合成：
以L-氨基丙醇代替实例1中的L-苯甘氨醇，其余同实施例1，得到氨基噻唑啉配体I-e，黄色油，产率55%，其核磁质谱数据如下：
1H NMR(300MHz,CDCl3)δ7.48(ddd,J=7.8,1.5,0.4Hz,1H),7.24–7.13(m,1H),6.75–6.63(m,2H),6.24(br s,2H),4.90–4.74(m,1H),3.41(dd,J=10.7,8.0Hz,1H),2.92(dd,J=10.7,7.7Hz,1H),1.47(d,J=6.7Hz,3H).13C NMR(75MHz,CDCl3)δ166.97,147.38,131.99,131.15,115.86,115.66,114.55,72.85,37.82,20.62.
高分辨质谱数据：ESI-HRMS Calcd for C10H13N2S[M+H]+:193.0794,Found:193.0796.
实施例6：不对称烯丙基烷基化
[Pd(η3-C3H5)Cl]2(0.0125mmol)，无水KOAc(0.1mmol)和手性氨基噻唑啉配体I-e(0.03mmol)在氮气保护下于二氯甲烷(2.0mL)中搅拌0.5h。在室温下，加入(E)-1,3-二苯基-2-烯丙基乙酸酯的二氯甲烷溶液(1.0mL)，接着加入丙二酸甲酯(0.17mL，1.5mmol)和BSA(0.37mL,1.5mmol)。室温搅拌24h后，用10mL饱和氯化铵溶液淬灭反应，分出有机相，水相用乙酸乙酯萃取（2×10mL），合并有机相，无水硫酸钠干燥。减压蒸去溶剂，剩余物经硅胶柱层析分离（石油醚/乙酸乙酯=5/1,v/v），得到无色油。88%收率，92%ee值(DaicelChiralcel AD-H,n-hexane/i-PrOH=90:10,1.0mL/min,254nm):tR(minor)=14.43min,tR(major)=19.77min）。1H NMR(300MHz,CDCl3):δ7.35-7.17(m,10H,Ar-H),6.47(d,J=15.75Hz,1H,-CH=),6.32(dd,J=8.43Hz,15.90Hz,1H,-CH=),4.26(dd,J=8.43Hz,10.80Hz,1H,CH),3.95(d,J=10.80Hz,1H,CH),3.71(s,3H,-OCH3),3.52(s,3H,-OCH3)。

Claims (6)

1.一种氨基噻唑啉手性配体化合物，其特征在于，该配体化合物具有苯环为骨架的手性邻氨基噻唑啉结构，结构通式如下：
式I中：
R1和R3为氢；
R2选自甲基，异丙基，异丁基，苯基和苄基，噻唑啉环上4位为S构型手性碳原子。
2.根据权利要求1所述的氨基噻唑啉手性配体化合物的制备方法，其特征在于，所述方法以邻硝基苯甲酸为原料，依次历经酰化、酰胺化和环化/还原三个步骤，“一锅法”合成；
所述的三个步骤依次是酰化、酰胺化、环化/还原，“一锅法”合成，反应式及步骤如下：
(1)酰化：将邻硝基苯甲酸和酰化试剂二氯亚砜、草酰氯、五氯化磷或三氯氧磷按摩尔比1:(1.2～20)在0～100℃反应0.5～24h，即得到相应的酰氯中间体；
(2)酰胺化：将步骤(1)得到酰氯中间体和相应的手性氨基醇按摩尔比1:(1.2～5)加入到惰性有机溶剂四氢呋喃、二氯甲烷或氯仿中，在过量的有机碱：吡啶、三乙胺或DBU；或无机碱：NaOH或NaHCO3存在下，于室温～-78℃搅拌反应0.5～24h，即生成羟基酰胺II，其中R为R2；
(3)环化/还原：将步骤(2)得到的羟基酰胺II和五硫化二磷按摩尔比1:(2～10)加入到惰性溶剂甲苯或苯中，在有机碱吡啶或三乙胺的存在下，80～120℃搅拌反应2～48h，即生成相应的胺基噻唑啉配体化合物；其中式I中：
R1和R3为氢；
R2选自甲基，异丙基，异丁基，苯基和苄基，噻唑啉环上4位为S构型手性碳原子。
3.根据权利要求2所述的氨基噻唑啉手性配体化合物的制备方法，其特征在于，所述步骤(1)中邻硝基苯甲酸是市售的。
4.根据权利要求2所述的氨基噻唑啉手性配体化合物的制备方法，其特征在于，所述步骤(2)中惰性有机溶剂四氢呋喃、二氯甲烷或氯仿的用量是手性氨基醇摩尔量的20～200倍。
5.根据权利要求2所述的氨基噻唑啉手性配体化合物的制备方法，其特征在于，所述步骤(3)的反应中，分子内脱水关环的同时，硝基被还原成氨基。
6.根据权利要求2所述的氨基噻唑啉手性配体化合物的制备方法，其特征在于，所述步骤(3)的反应中，惰性溶剂苯或甲苯的用量是羟基酰胺II摩尔量的40～100倍，有机碱吡啶或三乙胺的用量是羟基酰胺II摩尔量的4～30倍。
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