从Dibenzo-7-phosphanorbornadiene化合物中转移素的机制和范围
Wesley J Transue1, Alexandra Velian1, Matthew Nava1
1Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|July 14, 2017
概括
双-7-甲化合物作为有效的素来源. 基胺替代剂对于基的成功转移至关重要,使基和基的新合成途径成为可能.
科学领域:
- 有机化学
- 合成有机化学
- 反应机制研究
背景情况:
- 素是有机化学中至关重要的高反应性中间体.
- 在温和条件下生成和表征素仍然是一个重大挑战.
- Dibenzo-7-phosphorbornadiene衍生物为素生成提供了一个有前途的平台.
研究的目的:
- 为了研究二-7-化化合物作为化的前体.
- 阐明替代剂在素转移效率中的作用.
- 探索这些前体产生的新合成胺的应用.
主要方法:
- 双-7-甲衍生物的热分解
- 替代剂对素转移的影响分析.
- 分子束质谱 (MBMS) 用于检测素.
- 使用捕获剂 (1,3-环二烯,-d6) 的动态研究.
- 密度函数理论 (DFT) 计算用于机械洞察.
主要成果:
- 在70-90°C的温度下,通过热诱导的甲酸脱离会从二-7-甲基的前体生成素.
- 对于有效的素转移而言,π-捐赠型基胺基是必不可少的,而体质量也起着作用.
- 通过MBMS可以直接检测二甲基胺 ([Me2NP]).
- 动力数据和DFT计算支持一种涉及单分子碎片化为自由单片氨基胺的机制.
- 扩大了素受体范围,包括和,产生氨基替代和.
- 立体选择性素转移到烯表明单基碳类反应性.
结论:
- Dibenzo-7-phosphorbornadiene衍生物是产生aminophosphiniden的有效和可调的前体.
- 基胺替代剂显著提高了素转移效率.
- 这项研究提供了一种新的合成方法,用于获取有价值的氨基替代异环.
- 这些发现为进一步的气相光谱研究铺平了道路.
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