二 (II) /DPPM 催化1,2-基化结合二烯与三级基
Liqun Yang1, Xiaoyu Wu1, Wenkui Lu1
1Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Organic letters
|March 8, 2024
概括
这项研究引入了一种新的催化反应,用于使用三级西兰酸对二烯的区域选择性化. 该过程产生了有价值的同质基,避免了复杂的中间体.
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:
- 水化是有机合成中的一个关键反应,用于引入含的基.
- 在对合二烯的水化过程中,区域选择性控制仍然是一个挑战.
- 了解涉及过渡金属催化剂的反应机制对于开发高效的合成方法至关重要.
研究的目的:
- 开发一种简单而高效的方法,用于对联二烯的区域选择性1,2-抗马尔科夫尼科夫化.
- 研究反应机制,特别是过渡金属中间体的作用.
- 通过使用易于获得的试剂合成有价值的同质性西兰体.
主要方法:
- 使用了一种包含Rh2(OAc) 4和DPPM (双二) 甲) 的催化系统.
- 在乙酸中与各种联二烯和三级烯进行了反应.
- 进行控制实验以阐明反应途径并确定关键中间体.
主要成果:
- 对于1,2-抗马尔科夫尼科夫添加产品,实现了高区域选择性,产生同质的西兰酸盐.
- 在基板中对广泛的功能群体表现出耐受性.
- 观察到的二化物种,表明直接插入Rh-H键的机制,并排除了π-基过渡金属中间体.
结论:
- Rh2(OAc) 4/DPPM系统提供了一个高效的途径,以区域选择性1,2-抗马尔科夫尼科夫的合二烯的水化.
- 反应是通过将基直接插入化键进行的,不涉及π-基中间体.
- 合成的同质基烯是与各种功能组兼容的多功能构建块.
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