Vaulted Biaryls in Catalysis: A Structure-Activity Relationship Guided Tour of the Immanent Domain of the VANOL Ligand
Vaulted Biaryls in Catalysis: A Structure-Activity Relationship Guided Tour of the Immanent Domain of the VANOL Ligand
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DOI：
10.1002/chem.201302451
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发表时间：
2013-11-11
影响因子：
4.3
通讯作者：
Wulff, William D.
中科院分区：
文献类型：
--
作者：
Guan, Yong;Ding, Zhensheng;Wulff, William D.
BOROX催化剂中的活性位点是手性聚硼酸根阴离子（硼氧烷酸根），其通过底物分子由三当量的B（OPh）（3）和一个VANOL配体原位组装。底物通过与氧原子O 1-O3的H键与硼氧烷酸盐结合。在氮杂环丙烷化反应中，系统地研究了在VANOL配体的萘核的每个位置引入取代基的影响。在4，4-和8，8-位上的取代基对催化剂性能具有负面影响，而在7-和7-位上的取代基在正面方向上具有最大影响。
The active site in the BOROX catalyst is a chiral polyborate anion (boroxinate) that is assembled in situ from three equivalents of B(OPh)(3) and one of the VANOL ligand by a molecule of substrate. The substrates are bound to the boroxinate by Hbonds to oxygen atoms O1-O3. The effects of introducing substituents at each position of the naphthalene core of the VANOL ligand are systematically investigated in an aziridination reaction. Substituents in the 4,4- and 8,8-positions have a negative effect on catalyst performance, whereas, substituents in the 7- and 7-positions have the biggest impact in a positive direction.