Shynthesis of Carbocyclic Nucleosides Having Biological Function

1. 研究了顺式3,5-二取代环戊烯顺式二羟基化生成碳环核苷的反应。其立体选择性是由环戊烯取代基的构象决定的。研究了分子氟在双环[2.2.1]庚-2-烯衍生物上的加成和含氟碳环核苷的转化。这些核苷的生物学评价未显示出任何抗hiv活性。利用手性路易斯酸，研究了苯磺酰氰化物与环戊二烯的不对称Diels-Alder反应，得到了具有光学活性的2-氮杂环[2.2.1]庚-5-烯-3- 1，这是一种手性碳环核苷的合成物。由亚硝基烯和酮类合成的环硝基酮与冰片二烯或双环酰胺的1,3-偶极环加成反应，立体选择性地得到了外环加合物，这些外环加合物可能是合成含有α -氨基酸残基的碳环核苷的中间体。合成了一种新的二亲试剂——二甲基三氟乙酰氨基甲基丙烯酸酯。亲二烯试剂很容易与环戊二烯反应生成双环化合物，生成碳环同核苷。腺苷脱氨酶在高压下对碳环腺嘌呤核苷进行脱胺反应，表明该脱胺反应是外消旋碳环核苷动力学拆分的有效方法。

1. The cis-dihydroxylation of cis-3,5-disubstituted cyclopentenes leading to carbocyclic nucleosides was examined. Its stereoselectivity was found to be attibutable to the conformation of substituents of cyclopentenes.2. Addition of molecular fluorine to bicyclo [2.2.1] hept-2-ene derivatives and conversion to fluorine-containing carbocyclic nucleosides were carried out. Biological evaluation of these nucleosides did not show any anti-HIV activity.3. Asymmetric hetero Diels-Alder reaction of benzenesulfonyl cyanide with cyclopentadiene using chiral Lewis acids was investigated to give opticaliy active 2-azabicyclo [2.2.1] hept-5-en-3-one, which was a synthon of chiral carbocyclic nucleosides.4. The 1,3-dipolar cycloaddition reaction of bornadiene or bicycloamides with cyclic nitrones obtained from nitrosoketene with ketones gave stereoselectively the exocycloadducts, which would be intermediates for the synthesis of carbocyclic nucleosides containing an alpha-amino acid residue.5. A new dienophile, dimethyl trifluoroacetylaminomethylenemalonate, was created. The dienophile reacted readily with cyclopentadiene to give a bicyclic compound leading to carbocyclic homo-nucleosides.6. Deamination of carbocyclic adenine nucleosides by adenosine deaminase under highpressure revealed that the deamination was a useful procedure for the kinetical resolution of racemic carbocyclic nucleosides.