新型［1,2,4］-三唑并-A-homo-甾体杂环化合物的合成研究
摘要
甾体化合物及其衍生物广泛的存在于自然界,与许多生命过程密切相关。随着对其需求量的大量增加,依靠提取天然产物的甾体已经无法满足人们的需要,目前已逐步走向人工合成。由于生物活性多样性伴随着化学结构多样性,当甾体中的某个或几个C被N取代的时候(azasteroids),往往会出现新的活性。甾体A氮杂卓就是其中的一类,本文发展了一种全新的甾体A氮杂卓合成方法,与以往的报道相比,本文所合成的产物具有新颖的稠合模式及取代种类。
论文第一章介绍了天然甾体化合物的种类,对迄今为止甾体A氮杂卓的主要用途和合成方法进行了综述。此外,简述了1,3-偶极环加成和偶氮基碳正离子的研究概况和在构建含氮五员环中的应用。
论文第二章介绍了[1R-[1α(R*),3aβ,3bα,5aβ,12aα,12bβ,14aα]]-1-(1,5-二甲基己基)-1,2,3,3a,3b,4,5,11,12,12a,12b,13,14,14a-十四氢-8-取代-12a，144a-二甲基-9-(2,4,6-三氯苯基)-环戊烷并[5,6]萘烷并[2,1-d][1,2,4]三唑并[1,5-a]氮杂卓六氯化锑盐58的合成研究。我们首先对二氢胆固酮的三氯苯腙,进行α-氯代,在Lewis酸作用下脱氯,原位生成活泼的偶氮基碳正离子,并与腈发生极化环加成,升温后发生1,2-迁移重排。经过该反应序列,在甾体六员A环插入了一个N原子,扩环成氮杂卓环,并以此N原子作为桥原子之一并合了一个1,2,4-三唑环。我们对其中的一个产物58a进行了单晶培养和X-单晶衍射,产物的结构得到确证,并据此推测了反应机理。
在成功合成了三哗并氮杂卓六氯化锑盐的基础上,我们又成功的将该策略拓展,用于合成中性的三唑并氮杂卓66。以二氢胆固酮的乙氧羰基腙出发,经过类似的路线,最终合成另一系列的氮杂卓化合物。通过对比反应结果,我们发现不同的底物,其偶氮基正离子的反应活性不一样,此外不同的亲偶极体腈或炔,其反应能力也不一样。此后我们对合成路线中涉及到的关键步骤：1,3-偶极环加成和1,2-迁移重排,进行了机理讨论。
本章的最后一节我们仍以二氢胆固酮,经过α酰基化和缩合环加成合成出另一种甾体A并杂环的衍生物：胆甾烷并[3,2-c]-吡化合物。
论文第三章介绍了[1,2,4]-三唑并[1,5-a][1]苯并氮杂卓和[1,2,4]-三唑并[1,5-a]-喹啉的合成。我们希望把第二章介绍的合成三唑并杂环的路线方法推广到更多的环酮体系。从α-四氢萘酮的乙氧羰基腙74出发,经过乙酰氧基化、Lewis酸脱乙酰氧基、极化环加成、1,2-迁移重排,合成出相应的扩环产物：[1,2,4]-三唑并[1,5-a][1]苯并氮杂卓80。
从2,3-二氢-1-茚酮腙81出发,经过相同的路线,合成出相应的扩环产物[1,2,4]-三唑并[1,5-a]-喹啉87。对比两组实验结果,我们发现相同条件下5→6扩环比6→7扩不环更容易。但是我们试图把这一路线方法推广到酮体系,期望得到4→5员环的扩环产物：[1,2,4]-三唑并[1.2-b]-吡咯烷。但尚未获得满意结果。
论文第四章是实验部分,介绍了化合物的详细合成方法,记录了化合物的红外、核磁、高分辨质谱和元素分析数据。
Steroids and related derivatives occur widely in nature. Their significance connected with many life processes has well been documented. However, the traditional extraction method for achieving steroidal natural products cannot meet with the ever increasing utilities of this class of compounds, thus the development of new synthetic methods has become a necessity. The diversity of biological activity is associated with the diversity of chemical structure. For example, steroids in which one or several C replaced by one or more nitrogen atoms (leading to azasteroids) often put up a new activity. In particular, conversion of the steroidal A-ring into azepine ring has proved to be a valuable change. The present dissertation describes a novel and efficient methods for accessing a series of3-aza-A-homocholestane derivative, which show unprecedented characters both in the fusion mode and substitution pattern.
The first chapter summarizes the classification of steroidal natural products, with focus on the uses and synthetic methods of A-azepine-steroids. In addition, the research in the field of1,3-dipolar cycloadditions with the1-aza-2-azoniaallenium ions as cationic1,3-dipoles are briefly reviewed. Especially, the application of these newly emerging reactive intermediates in the assembly of N-containing five-membered heterocycles is introduced.
The second chapter describes firstly the synthesis of the precedentless pentacyclic compounds, i.e.[1R-[1α(R*),3aβ,3bα,5aβ,12aα,12bβ,14aα]]-1-(1,5-dimethylhexyl)-1,2,3,3a,3b,4,5,11.12,12a.12b.13.14,14a-tetradecahydro-8-sub stitued-12a,14a-dimethyl-9-(2,4,6-trichlorophenyl)-cyclopenta[5,6]naphtho[2,1-d][1,2,4]triazolo[1,5-a]azepinium hexachloroantimonates58. Starting from the easily available dihydrocholesteranone50, the2,4,6-trichlorophenyl hydrazone53was prepared by the usual condensation method. The a-chlorination of53with t-BuOCl as the chlorination agent gave the corresponding a-chloroazo compound55in96%yield. Then, dechlorination under the action of a Lewis acid like SbCl5generated the short-lived1-aza-2-azoniaallenium salt56, which underwent the cycloaddition with the pre-added nitrile with spontaneous1,2-shift rearrangement. This reaction sequently resulted in the insertion of an N atom in the six-membered A ring. Thus, this constitutes a new and efficient strategy leading to the formation of the triazolo fused A-aza-homocholesterane derivatives58. To ultimately ascertain the structural determination, single crystals of one of the products, namely58a, was grown and subjected to X-ray diffraction analysis, whereby providing unerring structural proof.
On the bases of the above results, and for the sake of future physiological activity evaluation, we modified our method to the synthesis of the neutral [1,2.4]triazolo[1,5-a]azepine analogies. Thus. the (5α)-cholestan-3-one's ethoxycarbonyl hydrazone60was prepared and allowed to react as described for58. Under comparable conditions. a set of [1,2,4]-triazolo-annulated3-aza-A-homocholestane compounds65or their picrates66were obtained in moderate yields. It has been observed that different substituted1-aza-2-azoniaallenium salts exhibited variable reactivity in this polar cycloaddition. Similarly, the nitrile or alkyne dipolarophiles behaved quite differently depending on the different stereo and electronic feature. According to our experimental data, together with investigations from our previous work, the mechanism with respect to the polar1,3-dipolar cycloaddition and1,2-shift were discussed.
Besides this study, we attempted the transformation of (5α)-cholestan-3-one to a-acylated products68which were condensed with hydrazine to furnish the pyrazolo fused cholestane derivatives70. Scope and limitations of this synthesis remains to be investigated.
In the third chapter, the application of azocarbenium ions for the synthesis of1,2,4-triazolo annulated bi-or tricyclic heterocycles was explored.. Thus,[1,2,4]-triazolo-[1,5-a][1]benzazepines80and [1,2,4]triazolo-[1,5-a]quinoline derivatives86were successfully synthesized starting from a-tetralone and2,3-dihydro-1-indanone. Oxidation of a-tetralone ethoxycarbonylhydrazone74with lead tetraacetate afforded the bicyclic geminal ethyl azoester75. On addition of equimolecular aluminum trichloride, the azocarbenium salt76was believed to be generated in situ as a reactive intermediate, which could be trapped to the C=N triple bond of the pre-added nitriles by cycloaddition. These cycloadducts underwent smooth1,2-aryl-shift with concurrent ring enlargement and insertion of a nitrogen atom to the carbon skeleton to afford the [1,2,4]-triazolo-[1,5-a][1]benzazepinium picrates80in23～56%yields, upon hydrolytic removal of the N-ethoxycarbonyl group and subsequent treatment of the alkalescent heterocycles with picric acid finally. Analogously, the novel4,5-dihydro-[1,2,4]-triazolo-[1,5-a] quinolinium picrates87have also been prepared starting from2,3-dihydro-1-indanone in moderate overall yields. In light of the above results, we concluded that under the same conditions the ring-expansion5→6seems to proceed more readily than that of6→7. Efforts were also made to extend this approach to the cyclobutanone system, aiming at achieving4→5membered-ring expansion to yield [1.2.4]-triazolo-[1,2-b]-pyrrolidines. However, all experiments failed so far.
The fourth chapter is the experiment part, providing the details both in the experimental procedures and characterization data including IR. NMR. HRMS and/or microelemental analysis.
论文第一章介绍了天然甾体化合物的种类,对迄今为止甾体A氮杂卓的主要用途和合成方法进行了综述。此外,简述了1,3-偶极环加成和偶氮基碳正离子的研究概况和在构建含氮五员环中的应用。
论文第二章介绍了[1R-[1α(R*),3aβ,3bα,5aβ,12aα,12bβ,14aα]]-1-(1,5-二甲基己基)-1,2,3,3a,3b,4,5,11,12,12a,12b,13,14,14a-十四氢-8-取代-12a，144a-二甲基-9-(2,4,6-三氯苯基)-环戊烷并[5,6]萘烷并[2,1-d][1,2,4]三唑并[1,5-a]氮杂卓六氯化锑盐58的合成研究。我们首先对二氢胆固酮的三氯苯腙,进行α-氯代,在Lewis酸作用下脱氯,原位生成活泼的偶氮基碳正离子,并与腈发生极化环加成,升温后发生1,2-迁移重排。经过该反应序列,在甾体六员A环插入了一个N原子,扩环成氮杂卓环,并以此N原子作为桥原子之一并合了一个1,2,4-三唑环。我们对其中的一个产物58a进行了单晶培养和X-单晶衍射,产物的结构得到确证,并据此推测了反应机理。
在成功合成了三哗并氮杂卓六氯化锑盐的基础上,我们又成功的将该策略拓展,用于合成中性的三唑并氮杂卓66。以二氢胆固酮的乙氧羰基腙出发,经过类似的路线,最终合成另一系列的氮杂卓化合物。通过对比反应结果,我们发现不同的底物,其偶氮基正离子的反应活性不一样,此外不同的亲偶极体腈或炔,其反应能力也不一样。此后我们对合成路线中涉及到的关键步骤：1,3-偶极环加成和1,2-迁移重排,进行了机理讨论。
本章的最后一节我们仍以二氢胆固酮,经过α酰基化和缩合环加成合成出另一种甾体A并杂环的衍生物：胆甾烷并[3,2-c]-吡化合物。
论文第三章介绍了[1,2,4]-三唑并[1,5-a][1]苯并氮杂卓和[1,2,4]-三唑并[1,5-a]-喹啉的合成。我们希望把第二章介绍的合成三唑并杂环的路线方法推广到更多的环酮体系。从α-四氢萘酮的乙氧羰基腙74出发,经过乙酰氧基化、Lewis酸脱乙酰氧基、极化环加成、1,2-迁移重排,合成出相应的扩环产物：[1,2,4]-三唑并[1,5-a][1]苯并氮杂卓80。
从2,3-二氢-1-茚酮腙81出发,经过相同的路线,合成出相应的扩环产物[1,2,4]-三唑并[1,5-a]-喹啉87。对比两组实验结果,我们发现相同条件下5→6扩环比6→7扩不环更容易。但是我们试图把这一路线方法推广到酮体系,期望得到4→5员环的扩环产物：[1,2,4]-三唑并[1.2-b]-吡咯烷。但尚未获得满意结果。
论文第四章是实验部分,介绍了化合物的详细合成方法,记录了化合物的红外、核磁、高分辨质谱和元素分析数据。
Steroids and related derivatives occur widely in nature. Their significance connected with many life processes has well been documented. However, the traditional extraction method for achieving steroidal natural products cannot meet with the ever increasing utilities of this class of compounds, thus the development of new synthetic methods has become a necessity. The diversity of biological activity is associated with the diversity of chemical structure. For example, steroids in which one or several C replaced by one or more nitrogen atoms (leading to azasteroids) often put up a new activity. In particular, conversion of the steroidal A-ring into azepine ring has proved to be a valuable change. The present dissertation describes a novel and efficient methods for accessing a series of3-aza-A-homocholestane derivative, which show unprecedented characters both in the fusion mode and substitution pattern.
The first chapter summarizes the classification of steroidal natural products, with focus on the uses and synthetic methods of A-azepine-steroids. In addition, the research in the field of1,3-dipolar cycloadditions with the1-aza-2-azoniaallenium ions as cationic1,3-dipoles are briefly reviewed. Especially, the application of these newly emerging reactive intermediates in the assembly of N-containing five-membered heterocycles is introduced.
The second chapter describes firstly the synthesis of the precedentless pentacyclic compounds, i.e.[1R-[1α(R*),3aβ,3bα,5aβ,12aα,12bβ,14aα]]-1-(1,5-dimethylhexyl)-1,2,3,3a,3b,4,5,11.12,12a.12b.13.14,14a-tetradecahydro-8-sub stitued-12a,14a-dimethyl-9-(2,4,6-trichlorophenyl)-cyclopenta[5,6]naphtho[2,1-d][1,2,4]triazolo[1,5-a]azepinium hexachloroantimonates58. Starting from the easily available dihydrocholesteranone50, the2,4,6-trichlorophenyl hydrazone53was prepared by the usual condensation method. The a-chlorination of53with t-BuOCl as the chlorination agent gave the corresponding a-chloroazo compound55in96%yield. Then, dechlorination under the action of a Lewis acid like SbCl5generated the short-lived1-aza-2-azoniaallenium salt56, which underwent the cycloaddition with the pre-added nitrile with spontaneous1,2-shift rearrangement. This reaction sequently resulted in the insertion of an N atom in the six-membered A ring. Thus, this constitutes a new and efficient strategy leading to the formation of the triazolo fused A-aza-homocholesterane derivatives58. To ultimately ascertain the structural determination, single crystals of one of the products, namely58a, was grown and subjected to X-ray diffraction analysis, whereby providing unerring structural proof.
On the bases of the above results, and for the sake of future physiological activity evaluation, we modified our method to the synthesis of the neutral [1,2.4]triazolo[1,5-a]azepine analogies. Thus. the (5α)-cholestan-3-one's ethoxycarbonyl hydrazone60was prepared and allowed to react as described for58. Under comparable conditions. a set of [1,2,4]-triazolo-annulated3-aza-A-homocholestane compounds65or their picrates66were obtained in moderate yields. It has been observed that different substituted1-aza-2-azoniaallenium salts exhibited variable reactivity in this polar cycloaddition. Similarly, the nitrile or alkyne dipolarophiles behaved quite differently depending on the different stereo and electronic feature. According to our experimental data, together with investigations from our previous work, the mechanism with respect to the polar1,3-dipolar cycloaddition and1,2-shift were discussed.
Besides this study, we attempted the transformation of (5α)-cholestan-3-one to a-acylated products68which were condensed with hydrazine to furnish the pyrazolo fused cholestane derivatives70. Scope and limitations of this synthesis remains to be investigated.
In the third chapter, the application of azocarbenium ions for the synthesis of1,2,4-triazolo annulated bi-or tricyclic heterocycles was explored.. Thus,[1,2,4]-triazolo-[1,5-a][1]benzazepines80and [1,2,4]triazolo-[1,5-a]quinoline derivatives86were successfully synthesized starting from a-tetralone and2,3-dihydro-1-indanone. Oxidation of a-tetralone ethoxycarbonylhydrazone74with lead tetraacetate afforded the bicyclic geminal ethyl azoester75. On addition of equimolecular aluminum trichloride, the azocarbenium salt76was believed to be generated in situ as a reactive intermediate, which could be trapped to the C=N triple bond of the pre-added nitriles by cycloaddition. These cycloadducts underwent smooth1,2-aryl-shift with concurrent ring enlargement and insertion of a nitrogen atom to the carbon skeleton to afford the [1,2,4]-triazolo-[1,5-a][1]benzazepinium picrates80in23～56%yields, upon hydrolytic removal of the N-ethoxycarbonyl group and subsequent treatment of the alkalescent heterocycles with picric acid finally. Analogously, the novel4,5-dihydro-[1,2,4]-triazolo-[1,5-a] quinolinium picrates87have also been prepared starting from2,3-dihydro-1-indanone in moderate overall yields. In light of the above results, we concluded that under the same conditions the ring-expansion5→6seems to proceed more readily than that of6→7. Efforts were also made to extend this approach to the cyclobutanone system, aiming at achieving4→5membered-ring expansion to yield [1.2.4]-triazolo-[1,2-b]-pyrrolidines. However, all experiments failed so far.
The fourth chapter is the experiment part, providing the details both in the experimental procedures and characterization data including IR. NMR. HRMS and/or microelemental analysis.
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