Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements
作者:Marcus Korb、Steve W. Lehrich、Heinrich Lang
DOI:10.1021/acs.joc.7b00030
日期:2017.3.17
temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)n(EAr)3–n (Fc = Fe(η5-C5H5)(η5-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1–3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles
阴离子磷酸弗里斯重排内的温度依赖行为的P(apFr)(O)(OFC)Ñ(EAR)3- Ñ(FC =铁(η 5 -C 5 H ^ 5)(η 5 -C 5 H ^ 4); E = O; Ar =苯基,萘基,(R)-BINOL,[3]二茂铁酰基; E = N,1 H-吡咯基,1 H-吲哚基,9 H-咔唑基; n = 1-3) 。当Fc经历一次时,基于Ph的apFr取决于温度。首先,芳基被锂化和重排,然后是Fc和N-杂环。我2 SO 4的加法因此得到甲基化的Fc,这与非有机金属芳族化合物形成HO和MeO衍生物的混合物相反。(R)-BINOL Fc磷酸酯以91%de得到Fc重排的膦酸酯。由于P处的电子密度较高,用N-脂族化合物交换O-阻止了apFr。还观察到1,2-N→C迁移。X射线分析证实了OH和NH衍生物的一维H桥键。通过电化学证实了N-脂族和N-芳族氨基磷酸酯之间反应性的差异。氧化还原电位显示