具有高活性,区域选择性和酶选择性基形成与由Bis-3,4-diazaphospholanes结合的Rh催化剂
Thomas P Clark1, Clark R Landis, Susan L Freed
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
研究人员开发了新的bis-3,4-diazaphospholane连接体,用于催化酶的酶选择性水合成型. 这些配体在温和条件下表现出高活性和选择性在转化 styrene,化和乙烯酸乙烯.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 有机合成 有机合成
背景情况:
- 开发高效的性配体对于不对称催化是至关重要的.
- 催化甲基化是化合成的关键工业过程.
- 酸联体为催化应用提供独特的结构特征.
研究的目的:
- 为了合成新的bis-3,4-diazaphospholane配体.
- 为了将这些连接体溶解成体纯净的形式.
- 为了评估它们在催化酶酶选择性水合甲基化中的性能.
主要方法:
- 亚酸与正甲基酸的反应,随后与1,2-二二二和酸乙烯的循环反应.
- 通过闪光色谱学分离二聚体胺基.
- 溶解联体在各种基质的Rh催化基化中的应用.
主要成果:
- 合成rac-bis-3,4-diazaphospholanes与酸组的合成.
- 通过二聚体胺形成,成功分离了等离子体.
- 高的催化活性和选择性 (高达95% ee,b:l比率> 30:1) 实现了烯,化和乙烯酸乙烯的化.
结论:
- 新的bis-3,4-diazaphospholane连接体对不对称的水合成型有效.
- 轻度反应条件和高周转频率 (约. 3000小时-1) 已经被证明.
- 这些配体代表了对酶选择性催化学的有前途的进展.
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