Nitrosation of 7-oxabicyclo[2.2.1]hept-5-en-2-exo-ylmethyl amine (20) gave 7-oxabicyclo[2.2.1]hept-5-en-2-exo-methanol (22) whereas 7-oxabicyclo[2.2.1]hept-5-en-2-endo-ylmethylamine (21) afforded a 1:1 mixture of 7-oxabicyclo[3.2.1]oct-6-en-2-ols (23) and 8-oxabicyclo[3.2.1]oct-3-en-2-ols (24). Nitrosations of 2-exo- (28) and 2-endo-aminomethyl-7-oxabicyclo[2.2.1]hept-5-en-2-ol (29) gave mixtures of 8-oxabicyclo[3.2.1]oct-6-en-2-one (25) and 8-oxabicyclo[3.2.1]oct-6-en-3-one (37). The preference for the C(3) methylene group migration giving 25 was the best (12:1) in the case of the 2-endo-aminomethyl alcohol29. Compared with the nitrosations of bicyclo[2.2.1]heptane analogues, the 7-oxa bridge in28and29enhances the preference for the C(3) methylene group migration vs. the C(1) methine group migration. The Tiffeneau-Demjanov one-carbon ring enlargement reactions of 2-exo-aminomethyl-7-oxabicyclo[2.2.1]hepta-2-endo-ol (30). 2-exo-aminomethyl-5-chloro (32) and 2-exo-aminomethyl-6-chloro-7-oxabicyclo[2.2.1]hept-5-en-endo-ol (33) are also reported. Under kinetically controlled conditions, 8-oxabicyclo[3.2.1]oct-6-en-2-one (25) adds to electrophiles EX=PhSeCl, PhSeBr. 2,4-(NO)₂C₆H₃SCl with high stereo- and regioselectivity giving the corresponding 8-oxabicyclo[3.2.1]-octan-2-ones where E substitutes the exo position of C(6) and X the exo position of C(7).

中文翻译：

---

2-氨基甲基-7-氧杂双环[2.2.1]庚烷衍生物的Demjanov和Tiffeneau-Demjanov一碳环扩大。8-氧杂双环[3.2.1] oct-6-en-2-one在亲电子试剂中的立体和区域选择性加成。

将7-氧杂双环[2.2.1]庚-5-en-2- exo - yl甲基胺（20）亚硝化得到7-氧杂双环[2.2.1] hept-5-en-2 -exo-甲醇（22），-氧杂双环[2.2.1]庚-5-烯-2-内基甲胺（21）提供了7-氧杂双环[3.2.1] oct-6-en-2-ols（23）和8的1：1混合物-氧杂双环[3.2.1] oct-3-en-2-ols（24）。的Nitrosations 2 -exo- （28）和2 -内氨基甲基-7-氧杂双环[2.2.1]庚-5-烯-2-醇（29）得到8-氧杂双环[3.2.1] oct-6-en-2-one（25）和8-氧杂双环[3.2.1] oct-6-en-3-one（37）的混合物。对于C-（3）亚甲基迁移给25的偏好是最好的（12：1）在2- endo-氨基甲醇29的情况下。与双环[2.2.1]庚烷类似物的亚硝化作用相比，在28和29中的7-氧杂桥可增强C（3）亚甲基迁移对C（1）次甲基迁移的偏好。2 -exo-氨基甲基-7-氧杂双环[2.2.1] hepta-2 -endo - ol的Tiffeneau-Demjanov一碳环扩大反应（30）。2外-氨基甲基-5-氯（32）和2 -exo-氨基甲基-6-氯-7-氧杂双环[2.2.1]庚-5-烯-内醇（33）也被报告。在动力学控制的条件下，将8-氧杂双环[3.2.1] oct-6-en-2-one（25）加到亲电试剂EX = PhSeCl，PhSeBr中。2,4-（NO）₂ C ₆ H ₃ SCl具有高的立体选择性和区域选择性，得到相应的8-oxabicyclocyclo [3.2.1] -octan-2-ones，其中E取代C（6）的外位，X取代C（7）的exo位置。