P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

P-Stereogenic monophosphines with the 2-p-terphenylyl and 1-pyrenyl substituents. Application to Pd and Ru asymmetric catalysis

“…From our previous studies [12,13,30] and from others [31,32],it is known that standard Jugé-Stephan [18] procedure isvery well suited to prepare P-stereogenic phosphines bearingo-monosubstituted aryl fragments. The introduction of the o-monosubstituted aryl fragment it is carried out via organolithiumsand therefore it is mandatory to have the suitable precursors toprepare such species.…”

“…We also devoted some effort to this field with the preparation ofseries of mono-and diphosphine ligands, which were used in Pd-catalysed reactions (hydrovinylation [10][11][12][13] and allylic alkylation [14]) and in Ru-catalysed (cyclopropanation [15] and hydrogentransfer [15,16]) enantioselective reactions. Although the opticallypure monophosphine ligands were initially obtained by resolutionof the racemic mixtures by means of Pd complexes [10,11], theyhave more recently obtained by methods based on asymmetric syn-thesis due to its superior versatility.…”

l‐Menthol‐Assisted Synthesis of P‐Stereogenic Phosphinous Acid Amides and Phosphine‐Boranes

“…A brief look at the possible transformations of analogous diastereomerically pure oxazaphospholidine‐boranes reveals that oxazaphospholidine ring opening with organolithium reagents is the only reaction that has been used to introduce carbon substituents at the phosphorus atom . Another method for modification of the structure would be dearomatization of the arene moiety, as developed in our research group for phosphine‐boranes and oxides .…”

“…The absolute configuration at phosphorus was assigned based on the literature precedent, which shows that methanolysis of phosphinous acid‐borane amides in the presence of a catalytic amount of acid proceeds with inversion of configuration at phosphorus. [16d] Compound ( S P )‐ 18 is a valuable substrate in the synthesis of P‐stereogenic phosphine ligands, so the development of an alternative method for the synthesis of this molecule should inspire chemists to search for new phosphine ligands.…”

Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions

“…To conclude, this methodology to prepare P-chirogenic modified EPHOS ligands derived from ephedrine, opens up further possibilities for optimizing and predict enantioselectivities in asymmetric catalyzed processes by designing AMPP* derived from aminoalcohols. -1982667, 1982668, 1982669, 1982665, 1982666, 1982663, 1982664, 1982661, 1982662, 1982659, 1982660, 1982656, 1982657, 1982658, 1982652, 1982653, 1982654, 1982650 and 1982651 The o-anisyl-, 11b -naphtyl-, 11b,29 -naphtyl-, 11b,29b o-tolyl-, 30,31 p-tolyl-, 31 o-biphenyl-, 11b,29,30 ferrocenyl-, 11b,14,30 t-butyl-, 11b,32 methyl-, 10,11b cyclohexyl-, 11b o- [(2methoxyethoxy)methoxy]phenyl-, 9b o-isopropoxyphenyl-, 31 3,5-xylyl-, 15 3,5-di-t-butylphenyl-, 33 2-(2',6'-dimethoxy)biphenyl-, 34 calix [4] arenyl-, 9c aminophosphines 11a-h, 11j-m, 11o, 11p, 11u, respectively, were prepared from the appropriate oxazaphospholidine-borane complex (+)-or (-)-10a or (-)-10b, according to the described procedure. These compounds exhibited satisfactory analytical and spectrochemical data in agreement with the literature.…”