作者:Anna I. Arkhypchuk、Marie-Pierre Santoni、Sascha Ott
DOI:10.1021/om201158k
日期:2012.2.13
Michaelis–Arbuzov conditions to give phosphinodiphosphonates 3a–e in quantitative yields. After complexation to W(CO)5 and treatment with CH3ONa, phospha-Wittig–Horner reagents 9a,b are obtained on a multigram scale in good overall yield. Phospha-Wittig–Horner reagents with unsaturated substituents at IIIP (10d,e) can be prepared in analogous procedures; however, they prevail in an unusual ylide form
P,P-二氯膦2a - c(RPCl 2,R = Ph(a),t -Bu(b),2,4,6-Me 3 Ph(c))和P,P-二溴膦4d,e(RPBr 2,R =(我-Pr)3 SiC≡C(d)和H 2 C = CH(ë))具有Michaelis-阿尔布佐夫条件下亚磷酸三乙酯反应,得到phosphinodiphosphonates 3A - ë以定量的产率。络合为W(CO)后如图5所示,用CH 3 ONa处理后,磷-维蒂希-霍纳试剂9a,b的克数为克,总收率良好。在III P(10d,e)处带有不饱和取代基的Phospha-Wittig-Horner试剂可以用类似的方法制备;然而,它们以不常见的内酯形式占优势,其分别允许孤对与乙炔和乙烯基π系统共轭。膦膦酸酯9a已经通过X射线晶体学表征,并且显示出在几分钟内与丙酮平滑反应。生成的W(CO)5取决于反应条件,显示出-α-配位的磷烯烃可二聚为1,