CN114671849B - 一种吡喃糖环的开环方法及其产品和应用 - Google Patents
一种吡喃糖环的开环方法及其产品和应用 Download PDFInfo
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Abstract
本发明涉及有机合成技术领域,公开了一种吡喃糖环的开环方法及其得到的开环衍生物,所述开环方法包括以下步骤:S1.以式Ⅰ所示的甲基‑α‑D‑吡喃葡萄糖苷为原料得到化合物Ⅱ;式中,R为Cl、Br、I或羟基;S2.所述化合物Ⅱ经开环反应,得到化合物Ⅲ;式中,R1为Cl、Br、I或乙酰氧基,R2为乙酰氧基、三氯乙酰氧基、丙酰氧基或苯甲酰氧基,R3为乙酰氧基、三氯乙酰氧基、丙酰氧基或苯甲酰氧基;本发明还公开了该开环方法或开环衍生物,在制备烯糖类化合物、肿瘤诊断试剂或肿瘤靶向药物上的应用;该开环方法通过将吡喃葡萄糖苷的2,3位磺酸酯化,形成了一种扭曲式的环状结构,极大地增强了吡喃环内张力,达到了反应条件温和、产率高并且对环境友好的效果。
Description
技术领域
本发明涉及有机合成技术领域,具体是一种吡喃糖环的开环方法及其产品和应用。
背景技术
糖类化合物广泛存在于自然界,是维持人体健康的营养元素之一,在生物体内有着许多种不同的作用。烯糖是指含有不饱和碳碳双键的糖。由于双键的存在,烯糖可以作为优良的合成子发生加成、氧化等反应,广泛的应用于各类糖苷、寡糖和生物大分子等的合成中。最经典的反应有Ferrier重排,它是合成各类糖苷的经典方法。此外,烯糖2位可以被不同基团取代,从而被进一步官能化。因此,烯糖在天然产物的全合成方面有着重要应用。
其中,具有吡喃糖骨架的含氧吡喃糖环是重要的碳水化合物衍生物,这些含氧吡喃糖环可作为天然糖类衍生物合成的优良底物。然而,目前打开含氧吡喃糖环的方法主要是将其和硫醇和硫酚反应,或使用路易斯酸对其进行催化。然而,上述方法均存在部分缺点:一方面,会产生大量带有刺激性气味的气体,对环境极不友好;另一方面,反应条件较为苛刻。
因此,我们亟需一种反应条件温和、产率高并且对环境友好的针对含氧吡喃糖环的开环方法。
发明内容
本发明的目的之一在于克服现有技术的不足,提供一种吡喃糖环的开环方法,以至少达到反应条件温和、产率高并且对环境友好的效果。
上述目的是通过以下技术方案来实现的:一种吡喃糖环的开环方法,包括以下步骤:
以式Ⅰ所示的甲基-α-D-吡喃葡萄糖苷为原料得到化合物Ⅱ;式中,R选自Cl、Br、I和羟基中的一种;
所述化合物Ⅱ经开环反应,得到化合物Ⅲ;R1选自Cl、Br、I和乙酰氧基中的一种,R2选自乙酰氧基、三氯乙酰氧基、丙酰氧基和苯甲酰氧基中的一种,R3选自乙酰氧基、三氯乙酰氧基、丙酰氧基和苯甲酰氧基中的一种。
在某些实施方案中,R为Cl、Br或I,步骤S1具体包括:
1)将二氯甲烷与磺酰氯混合,得到混合溶液Ⅰ;
2)取所述二氯甲烷与吡啶混合,滴加所述混合溶液Ⅰ,最后加入所述甲基-α-D-吡喃葡萄糖苷,在15~25℃下反应20~30h,得到化合物Ⅱ。
在某些实施方案中,步骤1)中,所述二氯甲烷和磺酰氯的体积比为10~15:1。
在某些实施方案中,步骤2)中,所述吡啶、甲基-α-D-吡喃葡萄糖苷和混合溶液Ⅰ中的磺酰氯的摩尔比为4~7:1:1.5~2.5。
在某些实施方案中,R为羟基,步骤S1具体包括:
取所述甲基-α-D-吡喃葡萄糖苷、N,N-二甲基甲酰胺、2,2-二甲氧基丙烷与催化剂混合,在35~45℃下反应15~25h,得到化合物Ⅳ;
2)取乙酸乙酯与磺酰氯混合,得到混合溶液Ⅱ;
取所述化合物Ⅳ、乙酸乙酯与三乙胺混合,滴加所述混合溶液Ⅱ,在15~25℃反应15~25h,得到化合物Ⅴ;
取所述化合物Ⅴ与甲醇混合,滴加浓硫酸,在15~25℃下反应2~4h,得到所述化合物Ⅱ。
在某些实施方案中,步骤1)中,所述甲基-α-D-吡喃葡萄糖苷、2,2-二甲氧基丙烷和催化剂的摩尔比为1:4~7:0.01。
在某些实施方案中,步骤2)中,所述乙酸乙酯和磺酰氯的体积比为40~60:1。
在某些实施方案中,步骤3)中,所述化合物Ⅳ、三乙胺和混合溶液Ⅱ中的磺酰氯的摩尔比为1:4~7:1.5~2.5。
在某些实施方案中,步骤4)中,所述甲醇和浓硫酸的体积比为5~10:1~2。
在某些实施方案中,步骤1)中,所述催化剂包括对甲苯磺酸。
在某些实施方案中,步骤4)中,所述浓硫酸的质量分数为95%~98%。
在某些实施方案中,步骤S2具体包括:将所述化合物Ⅱ与反应试剂混合,滴加浓硫酸,在15~25℃下进行开环反应3~4h,得到化合物Ⅲ。
在某些实施方案中,所述反应试剂和浓硫酸的体积比为5~10:1~2。
在某些实施方案中,所述浓硫酸的质量分数为95%~98%。
在某些实施方案中,所述反应试剂包括乙酸酐、三氯乙酸酐、苯甲酸酐和丙酸酐中的一种。
在本实施方案中,所述乙酸酐、三氯乙酸酐、苯甲酸酐和丙酸酐属于同系物,其作为开环酯化剂,主要通过捕获酸催化产生异头碳正离子,形成链酯化结构,符合同系物反应的相似性。
值得注意的是,本发明的开环方法通过将吡喃葡萄糖苷的2,3位磺酸酯化,形成了一种扭曲式的环状结构,极大地增强了吡喃环内张力;同时,利用环上的位阻和扭曲张力的作用,导致异头碳在受到亲电进攻时,容易形成开环结构释放环张力,从而仅在常温的酸性条件下即可实现吡喃糖环的开环,达到了反应条件温和、产率高并且对环境友好的效果。
本发明的目的之二在于提供上述开环方法制备得到的开环衍生物。
本发明的目的之三在于提供上述开环方法或开环衍生物,在制备烯糖类化合物、肿瘤诊断试剂或肿瘤靶向药物上的应用。
在某些实施方案中,所述制备烯糖类化合物是指:通过还原剂(如锌粉)对所述开环方法得到的开环衍生物进行还原,从而将所述开环衍生物中的磺酰基脱去形成烯糖结构。
在某些实施方案中,所述制备肿瘤诊断试剂包括以下步骤:
将所述化合物III与四氢呋喃混合,在15~25℃下加入浓盐酸,在30~40℃下反应15~20h,得到中间体Ⅵ;
将所述中间体Ⅵ、N,N-二甲基甲酰胺与苯甲醛缩二甲醇混合,滴加甲烷磺酸,在15~25℃下反应6~8h,得到化合物Ⅶ。
在上述实施方案中,所述化合物Ⅶ的结构(2)可以通过还原磺酸酯将2位上的羟基用苄基保护,再选择性水解脱除4,6位苄基,然后将羟基乙酰化,最后将2位苄基还原并用三氟甲磺酰基保护,从而高选择性、高收率地得到用作肿瘤诊断试剂的18F-FDG(氟代脱氧葡萄糖)。
需要注意的是,所述中间体Ⅵ和化合物Ⅶ均为不稳定状态,故而均会在(1)和(2)两种结构之间相互转化;其中,所述化合物Ⅶ的(1)和(2)两种结构的摩尔比为1:1。
在某些实施方案中,步骤S1中,所述四氢呋喃和浓盐酸的体积比为10~11:2。
在某些实施方案中,步骤S1中,所述浓盐酸的质量分数为36%~38%。
在某些实施方案中,步骤S2中,所述中间体Ⅵ、N,N-二甲基甲酰胺、苯甲醛缩二甲醇和甲烷磺酸的摩尔比为1:40~60:4~6:0.2~1。
在某些实施方案中,所述开环方法得到的开环衍生物在制备肿瘤靶向药物时的作用机理为:所述开环衍生物形成开链环磺酸酯结构,因其在化学性质方面具有优良的离去诱导碳正离子的作用,从而可以依据肿瘤细胞对糖高代谢的特点,释放高反应性的糖系衍生物,从而能够诱导肿瘤细胞的死亡。
应当理解的是,本发明中的反应条件,如各反应的温度和时间,仅以使反应完全为目的,可根据本领域技术人员的需要进行适应性调整。
本发明中的“和/或”是指,通过“和/或”连接的前后两个技术特征既可以为并列关系,也可以为择一选用关系。例如,“A和/或B”包含“A”、“B”和“A+B”三种情况。
本发明的有益效果是:本发明的一种吡喃糖环的开环方法,通过将吡喃葡萄糖苷的2,3位磺酸酯化,形成了一种扭曲式的环状结构,极大地增强了吡喃环内张力,利用环上的位阻和扭曲张力的作用,从而仅在常温的酸性条件下即可实现吡喃糖环的开环,达到了反应条件温和、产率高并且对环境友好的效果。
附图说明
图1为实施例1所得化合物Ⅱ的核磁共振氢谱图;
图2为实施例1所得化合物Ⅱ的核磁共振碳谱图;
图3为实施例1所得化合物Ⅲ的核磁共振氢谱图;
图4为实施例1所得化合物Ⅲ的核磁共振碳谱图;
图5为实施例2所得化合物Ⅳ的核磁共振氢谱图;
图6为实施例2所得化合物Ⅳ的核磁共振碳谱图;
图7为实施例2所得化合物Ⅴ的核磁共振氢谱图;
图8为实施例2所得化合物Ⅴ的核磁共振碳谱图;
图9为实施例2所得化合物Ⅱ的核磁共振氢谱图;
图10为实施例2所得化合物Ⅱ的核磁共振碳谱图;
图11为实施例2所得化合物Ⅲ的核磁共振氢谱图;
图12为实施例2所得化合物Ⅲ的核磁共振碳谱图;
图13为实施例3所得化合物Ⅶ的核磁共振氢谱图;
图14为实施例3所得化合物Ⅶ的核磁共振碳谱图。
具体实施方式
下面进一步详细描述本发明的技术方案,但本发明的保护范围不局限于以下所述。
实施例1
一种吡喃葡萄糖苷的开环方法,合成路线为:
包括以下步骤:
S1.按化学计量比将二氯甲烷(30mL)加入圆底烧瓶(100mL)中,加入5当量的吡啶(1.7mL,0.021mmol)。随后滴加含有磺酰氯(0.87mL,0.011mmol)的二氯甲烷溶液(10mL),加入甲基-α-D-吡喃葡萄糖苷(1g,0.005mmol),在常温(15~25℃)下反应24h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=7:3),将溶液过滤并减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=9:1)纯化,将组分浓缩得到化合物Ⅱ,为白色无定形固体(产量0.72g,47.7%)。
1H NMR(600MHz,CDCl3):δ5.34(dd,J=10.2,3.6Hz,1H),5.17(d,J=3Hz,1H),5.09(dd,J=10.2,3Hz,1H),4.76(d,J=3Hz,1H),4.24-4.22(m,1H),3.72-3.66(m,2H),3.57(s,3H).
13C NMR(150MHz,CDCl3):δ96.02,78.69,77.44,70.22,56.59,55.72,41.49.
S2.按化学计量比称量化合物Ⅱ(0.72g,0.003mmol)加入圆底烧瓶(50mL)中,随后加入乙酸酐(30mL),搅拌使其溶解,随后滴加5滴质量分数为95%的浓硫酸,在常温(15~25℃)下反应4h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=7:3),向体系中加入乙酸乙酯稀释,合并的有机层用盐水洗涤,经无水硫酸钠干燥,减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=5:1)纯化,将组分浓缩得到化合物Ⅲ,为澄清油状(产量1.38g,93.3%)。
1H NMR(600MHz,CDCl3):δ6.11(d,J=3Hz,1H),6.00(d,J=4.2Hz,1H),5.39-5.37(m,2H),5.07(t,J=3Hz,1H),5.02(dd,J=9,3Hz,1H),4.99-4.96(m,2H),4.77-4.74(m,2H),3.76(dd,J=11.4,5.4Hz,2H),3.67-3.64(m,2H),3.57(s,3H),3.53(s,3H),2.19-2.16(m,12H).
13C NMR(150MHz,CDCl3):δ170.34,169.83,169.19,169.16,94.50,93.18,81.06,81.01,78.6978.44,70.01,69.97,58.44,57.81,57.27,57.19,40.34,40.25,20.77,20.67,20.66.
实施例2
一种吡喃葡萄糖苷的开环方法,合成路线为:
包括以下步骤:
S1.按化学计量比称量甲基-α-D-吡喃葡萄糖苷(5g,0.026mmol)加入圆底烧瓶(500mL)中,随后加入N,N-二甲基甲酰胺(150mL)中,充分溶解后,在室温下加入2,2-二甲氧基丙烷(15.83mL,0.129mmol),以对甲苯磺酸作为催化剂(0.01g),在40℃下反应18h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=0:1),待体系冷却后,真空旋干N,N-二甲基甲酰胺,向体系中加入乙酸乙酯稀释,合并的有机层用盐水洗涤,经无水硫酸钠干燥,减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=1:1)纯化,将组分浓缩得到化合物Ⅳ,为澄清油状(产量4.45g,73.8%)。
1H NMR(600MHz,CDCl3):δ4.76(d,J=6Hz,1H),3.88(dd,J=10.8,5.4Hz,1H),3.80-3.73(m,2H),3.64-3.580(m,2H),3.52(t,J=9.6Hz,1H),3.42(s,3H),2.18(s,-OH),1.52(s,3H),1.44(s,3H).
13C NMR(150MHz,CDCl3):δ99.84,99.76,73.53,72.96,71.87,63.26,62.33,55.40,29.06,19.11。
S2.按化学计量比称量化合物Ⅳ(2g,0.009mmol)加入圆底烧瓶(500mL)中,随后加入干燥的乙酸乙酯(100mL)中,充分溶解后,加入5当量三乙胺(5.92mL,0.043mmol)。随后滴加含有磺酰氯(1.73mL,0.021mmol)的乙酸乙酯溶液(100mL),在常温(15~25℃)下反应18h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=7:3),将溶液过滤并减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=9:1)纯化,将组分浓缩得到化合物Ⅴ,为白色无定形固体(产量1.39g,55%)。
1H NMR(600MHz,CDCl3):δ5.12(d,J=3Hz,1H),5.08(t,J=9.6Hz,1H),4.59(dd,J=10.2,3Hz,1H),4.12(t,J=9.6Hz,1H),3.93-3.85(m,2H),3.76-3.72(m,1H),3.52(s,3H),1.54(s,3H),1.44(s,3H).
13C NMR(150MHz,CDCl3):δ100.32,96.01,80.82,80.72,71.98,66.17,61.83,56.13,28.72,19.02。
S3.按化学计量比称量化合物Ⅴ(1.3g,0.004mmol)加入圆底烧瓶(150mL)中,随后加入甲醇(80mL),充分溶解后,随后滴加4滴质量分数为98%的浓硫酸,在常温(15~25℃)下反应3h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=0:1),向体系中加入乙酸乙酯稀释,合并的有机层用盐水洗涤,经无水硫酸钠干燥,减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=3:2)纯化,将组分浓缩得到化合物Ⅱ,为白色无定形固体(产量0.97g,86.3%)。
1H NMR(600MHz,DMSO):δ5.75(s,2H,OH),5.24(d,J=1.8Hz,1H),4.93-4.97(m,2H),3.95-3.99(m,1H),3.69(dd,J=1.2,12Hz,1H),3.59(dd,J=5.4,12Hz,1H),3.44-3.46(m,1H),3.41(s,3H)
13C NMR(150MHz,DMSO):δ94.61,86.19,81.43,75.24,67.22,59.89,55.41.
S4.按化学计量比称量化合物Ⅱ(0.9g,0.004mmol)加入圆底烧瓶(50mL)中,随后加入乙酸酐(20mL),搅拌使其溶解,随后滴加5滴质量分数为98%的浓硫酸,在常温(15~25℃)下反应3h,通过薄层层析法判断反应完全(石油醚:乙酸乙酯=7:3),向体系中加入乙酸乙酯稀释,合并的有机层用盐水洗涤,经无水硫酸钠干燥,减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=5:1)纯化,将组分浓缩得到化合物Ⅲ,为澄清油状(产量1.41g,90.7%)。
1H NMR(600MHz,CDCl3):δ6.10(d,J=3Hz,1H),6.03(d,J=4.2Hz,1H),5.43(dd,J=1.8,9.8Hz,1H),5.37(dd,J=1.8,7.2Hz,1H),5.26-5.21(m,2H),5.21-5.17(m,2H),4.74(dd,J=3.6,6Hz,1H),4.57(dd,J=4.8,7.2Hz,1H),4.39-4.36(m,2H),4.24(dd,J=4.8,12.6Hz,2H),3.58(s,3H),3.52(s,3H),2.20(s,3H),2.18(m,9H),2.13(s,6H),2.07(d,J=2.4Hz,6H).
13CNMR(150MHz,CDCl3):δ170.35,170.32,170.17,169.96,169.94,169.72,169.58,169.49,93.99,93.11,79.11,79.06,78.9378.78,69.59,69.52,68.83,67.90,61.14,61.11,58.54,58.01,20.82,20.74,20.66,20.63,20.61,20.45.
实施例3
包括以下步骤:
S1.按化学计量比称量化合物III(1g,0.0023mmol)加入圆底烧瓶(50mL)中,随后加入10mL四氢呋喃中,充分溶解后,在室温加入2mL质量分数为38%的浓盐酸,35℃反应15h,通过薄层层析法判断反应完全(甲醇:乙酸乙酯=1:1),待体系冷却后,利用碳酸氢钠调Ph至5~7,减压蒸馏旋干,向体系中加入无水乙醇,过滤,减压浓缩得到中间体Ⅵ;
S2.向化合物Ⅵ(0.6g,0.0022mol)中加入5mL N,N-二甲基甲酰胺,充分溶解后,加入4倍苯甲醛缩二甲醇(1.31ml,0.0088mmol),滴加2滴甲烷磺酸,在室温(15~25℃)下反应6~8h。通过薄层层析法判断反应完全(石油醚:乙酸乙酯=0:1),向体系中加入乙酸乙酯稀释,合并的有机层用盐水洗涤,经无水硫酸钠干燥,减压蒸馏得到粗产物;粗产物通过硅胶柱色谱法(石油醚:乙酸乙酯=4:1)纯化,将组分浓缩得到化合物Ⅶ,为澄清油状(产量0.34g,47.05%)。
1HNMR(600MHz,CDCl3):δ10.01(s,1H,-CHO),7.50-7.47(m,4H),7.39-7.37(m,6H),5.58(s,1H),5.55(s,1H,-OH),5.36(s,1H),4.93(s,1H,-OH),4.47(dd,J=3.6,1.2Hz,1H),4.39(d,J=3.6Hz,1H),4.37(s,2H),4.35(dd,J=10.8,4.8Hz,1H),4.26(dd,J=10.2,4.8Hz,1H),4.13-4.09(m,2H),4.07(dd,J=9.6,4.2Hz,1H),3.98(t,J=9Hz,1H),3.89(t,J=9.6Hz,1H),3.83-3.80(m,2H),3.45-3.41(m,1H).
13C NMR(150MHz,CDCl3):δ192.58(-CHO),136.97,136.76,129.43,129.34,128.41,128.38,126.27,126.22,102.31(-CHPh),102.23(-CHPh),95.60,92.87,78.76,77.82,69.90,68.63,68.23,67.50,66.80,66.51,64.13,61.97.
以上所述仅是本发明的优选实施方式,应当理解本发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围,则都应在本发明所附权利要求的保护范围内。
Claims (10)
2.根据权利要求1所述的开环方法,其特征在于,R为Cl,步骤S1具体包括:
1)将二氯甲烷与磺酰氯混合,得到混合溶液Ⅰ;
2)取二氯甲烷与吡啶混合,滴加所述混合溶液Ⅰ,最后加入所述甲基-α-D-吡喃葡萄糖苷,在15~25℃下反应20~30h,得到化合物Ⅱ。
3.根据权利要求2所述的开环方法,其特征在于,步骤1)中,所述二氯甲烷和磺酰氯的体积比为10~15:1;
和/或,步骤2)中,所述吡啶、甲基-α-D-吡喃葡萄糖苷和混合溶液Ⅰ中的磺酰氯的摩尔比为4~7:1:1.5~2.5。
5.根据权利要求4所述的开环方法,其特征在于,步骤1)中,所述甲基-α-D-吡喃葡萄糖苷、2,2-二甲氧基丙烷和催化剂的摩尔比为1:4~7:0.01;
和/或,步骤2)中,所述乙酸乙酯和磺酰氯的体积比为40~60:1;
和/或,步骤3)中,所述化合物Ⅳ、三乙胺和混合溶液Ⅱ中的磺酰氯的摩尔比为1:4~7:1.5~2.5;
和/或,步骤4)中,所述甲醇和浓硫酸的体积比为5~10:1~2。
6.根据权利要求5所述的开环方法,其特征在于,步骤1)中,所述催化剂为对甲苯磺酸;和/或,步骤4)中,所述浓硫酸的质量分数为95%~98%。
7.根据权利要求1所述的开环方法,其特征在于,步骤S2具体包括:将所述化合物Ⅱ与反应试剂混合,滴加浓硫酸,在15~25℃下进行开环反应3~4h,得到化合物Ⅲ。
8.根据权利要求7所述的开环方法,其特征在于,所述反应试剂和浓硫酸的体积比为5~10:1~2;和/或,所述浓硫酸的质量分数为95%~98%;和/或,所述反应试剂为乙酸酐。
9.根据权利要求1~8任一项所述的开环方法制备得到的开环衍生物。
10.权利要求9所述的开环衍生物在制备烯糖类化合物或肿瘤诊断试剂上的应用。
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