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环闭enyne元论:控制模式选择性和立体选择性
1Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Journal of the American Chemical Society
|November 19, 2004
概括
环闭 enyne 转移效率形成宏观循环. 乙烯大气改善了宏环二烯中内产物和E/Z异构体的选择性.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- 环闭enyne转化是宏循环合成的一个强大的工具.
- 在宏观循环中控制选择性仍然是一个挑战.
研究的目的:
- 开发一种选择性方法,通过环闭和内基转化合成10-15个成员的环.
- 调查影响xo/endo和E/Z选择性的因素.
主要方法:
- 使用酸盐衍生链接器连接一个和另一个子单元.
- 在不同的条件下,包括乙烯大气中,进行了环闭enyne转化反应.
- 根据环大小和反应条件分析产品选择性.
主要成果:
- 环形大小决定了外来/内在选择性:较大的环形 (12-15) 偏爱内在,较小的环形 (5-11) 偏爱外来.
- 乙烯大气层显著提高了宏环二烯的外/内选择性和E/Z选择性.
- 乙烯诱导交叉转移,导致二烯转移,这只会形成具有高E选择性的内分产物.
结论:
- 环闭enyne转移是宏观循环的一个可行的途径.
- 乙烯大气对于通过这种方法在宏循环化中实现高选择性至关重要.
- 描述的方法提供了对宏环二烯合成的精确控制.
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