Doherty Simon, Newman Colin R, Rath Rakesh K, Luo He-Kuan, Nieuwenhuyzen Mark, Knight Julian G
Centre for the Theory and Applications of Catalysis, School of Chemistry, The Queen's University of Belfast, David Keir Building, Stranmillis Road, Belfast, BT9 5AG, UK.
Org Lett. 2003 Oct 16;5(21):3863-6. doi: 10.1021/ol035409i.
[structure: see text] Palladium and platinum complexes of conformationally flexible 1,3-butadiene-bridged diphosphines NUPHOS can be resolved with (S)-BINOL at elevated temperatures to afford diastereopure delta-[(NUPHOS)M[(S)-BINOL]] (M = Pd, Pt). The homochiral Lewis acid complexes delta-[(NUPHOS)M]OTf, generated by protonation of delta-[(NUPHOS)M[(S)-BINOL]] with trifluoromethanesulfonic acid, catalyze the Diels-Alder reaction between acryloyl-N-oxazolidinones and cyclopentadiene to give ee values up to 96%. The corresponding enantiopure dichlorides delta-[(NUPHOS)PtCl(2)] react with AgClO(4) to form highly efficient catalysts that give good endo/exo selectivities and high endo enantioselectivity.
[结构：见正文] 构象灵活的1,3 - 丁二烯桥连二膦NUPHOS的钯和铂配合物在高温下可与(S)-联萘酚拆分，得到非对映纯的δ - [(NUPHOS)M[(S)-联萘酚]]（M = Pd，Pt）。通过用三氟甲磺酸质子化δ - [(NUPHOS)M[(S)-联萘酚]]生成的手性纯路易斯酸配合物δ - [(NUPHOS)M][OTf]₂，催化丙烯酰基 - N - 恶唑烷酮与环戊二烯之间的狄尔斯 - 阿尔德反应，对映体过量值高达96%。相应的对映纯二氯化物δ - [(NUPHOS)PtCl₂]与AgClO₄反应形成高效催化剂，具有良好的内型/外型选择性和高的内型对映选择性。
