铜催化分子间化和非激活基的化
Ba L Tran1, Bijie Li, Matthias Driess
1Department of Chemistry, University of California , Berkeley, California 94720, United States.
Journal of the American Chemical Society
|January 11, 2014
概括
本研究介绍了罕见的铜催化反应,用于从和胺中产生N-基产物. 该机制涉及三基基激素攻击C-H键,其次是基激素与铜中间体的组合.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 在有机合成中,开发有效的C-H功能化的方法至关重要.
- 铜催化为各种化学转化提供了一个多功能平台.
- 阿尔干的化仍然是一个具有挑战性的合成目标.
研究的目的:
- 报告使用简单基的胺,硫胺和胺的N-化新型铜催化反应.
- 阐明反应机制,包括确定关键中间体和基质物种.
- 为了研究C-H键功能化的选择性.
主要方法:
- 使用各种胺/胺基和基的铜催化化反应.
- 潜在的铜-甲胺中间体的分离和表征: [) Cu ) ] (1-) 和 [) Cu ) ] (1-2).
- 使用中间体,基因陷 (例如,CBr4) 和同位素标记 (d12-环) 的固体测量反应来探测机制.
- 动力学研究以确定限制营业额的步骤.
主要成果:
- 通过铜催化成功合成来自和胺/胺的N-基产物.
- 功能化主要发生在二级C-H键,而不是三级,甚至在初级C-H键.
- 证据支持一种机制,涉及tBuOOtBu产生的三基激素,这些激素从中抽取,形成基激素.
- 基随后与铜中间体 (1-phth2) 结合,产生N-基产物.
- 由三基基的C-H裂变被确定为营业额限制的步骤.
结论:
- 已经建立了一种新的铜催化途径,用于使用烯直接N-化胺和胺.
- 反应通过由三基基激素启动的基因机制进行,并涉及基基中间体.
- 该方法表明可控制的C-H功能选择性,为有机合成提供了有价值的工具.
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