Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str., 1, 53121, Bonn, Germany.
Dalton Trans. 2010 Dec 21;39(47):11445-50. doi: 10.1039/c0dt00730g. Epub 2010 Oct 26.
Atom efficient reactions of 3-ferrocenyl-2H-azaphosphirene complex 1 using a newly developed acid/base ring expansion protocol are presented. Consecutive reaction of 1 in the presence of dimethyl cyanamide with triflic acid and triethylamine yielded the selective formation of 2H-1,4,2-diazaphosphole complex 3. The same protocol using acetone, benzaldehyde and ferrocenyl aldehyde afforded 1,3,5-oxazaphosphol-3-ene complexes 4, 5a,b and 6a,b, the latter as mixtures of diastereomers, which could be separated. Apart from NMR, IR and UV/vis spectroscopic data, the single-crystal X-ray structures of complexes 3, 4 and 6a are discussed.
呈现了使用新开发的酸碱环扩缩反应体系，对 3-二茂铁基-2H-氮杂膦烯配合物 1 进行高效原子经济性反应。在三氟甲磺酸和三乙胺存在下，1 与二甲基氰酰胺连续反应，选择性生成了 2H-1,4,2-二氮杂磷杂环戊烯配合物 3。使用丙酮、苯甲醛和二茂铁甲醛的相同反应体系得到了 1,3,5-氧杂磷杂环戊烯配合物 4、5a,b 和 6a,b，后者为非对映异构体混合物，可以进行分离。除了 NMR、IR 和 UV/vis 光谱数据外，还讨论了配合物 3、4 和 6a 的单晶 X 射线结构。
