Enantioselective Pd-catalyzed C*–C, C*–N, and C*–S bond formation reactions using first P,P,N,N-tetradentate chiral phosphites

Phosphite-Containing Ligands for Asymmetric Catalysis

“…In 2005, chiral P,P,N,Ntetradentate ferrocene-derived iminophosphites 142 (Figure 47) were synthesized and applied in the Pd-catalyzed allylic substitution of 1,3-diphenyl-3-acetoxyprop-1-ene with dimethyl malonate (up to 86% ee) and pyrrolidine (up to 15% ee). 107 Subsequently, the same authors developed P,N-bidentate ferrocene-and cymantrene-based iminoarylphosphites 143 (Figure 47) for the Pd-catalyzed allylic substitution of 1,3diphenyl-3-acetoxyprop-1-ene with dimethyl malonate (ee's up to 97%) and sodium diformylamide (ee's up to 96%). 108 In 2007, the above-mentioned ferrocenyliminophosphite ligands 81 (Figure 23) were applied in the Pd-catalyzed allylic substitution of 1,3-diphenyl-3-acetoxyprop-1-ene with several nucleophiles (ee's up to 60%).…”

“…In 2005, chiral P , P , N , N -tetradentate ferrocene-derived iminophosphites 142 (Figure ) were synthesized and applied in the Pd-catalyzed allylic substitution of 1,3-diphenyl-3-acetoxyprop-1-ene with dimethyl malonate (up to 86% ee) and pyrrolidine (up to 15% ee) …”

Recent Applications of Chiral Ferrocene Ligands in Asymmetric Catalysis

“…In spite of its low interest from a synthetic‐applicability point of view, the Pd‐catalyzed asymmetric allylic alkylation (AAA) reaction140 of 1,3‐diphenylpropenyl acetate with soft nucleophiles has become a standard model reaction for the screening of newly designed ligand structures. Within the period covered by this review, more than twenty new ferrocene ligands with P,P,141 P,N‐,126, 142 P,S‐,41, 142a, 143 N,S‐,142a, n, 144 S,S‐,143b and P,P,N,N‐coordination145 modes have been tested in this benchmark reaction. Unfortunately, most of those ferrocene‐based chiral ligands appear to be confined to this particular reaction, since only in very few cases their successful application to more challenging substrates has been documented.…”

Chirale Ferrocenliganden in der asymmetrischen Katalyse

“…Die Pd‐katalysierte asymmetrische allylische Alkylierung (AAA)140 von 1,3‐Diphenylpropenylacetat mit weichen Nucleophilen hat sich zu einer Standardtestreaktion zur Untersuchung von neu entwickelten Ligandenstrukturen entwickelt. In dem Zeitraum, der in diesem Aufsatz abgedeckt ist, wurden mehr als zwanzig neue Ferrocenliganden in dieser Modellreaktion getestet, darunter P,P‐,141 P,N‐,126, 142 P,S‐,41, 142a, 143 N,S‐,142a, n, 144 S,S‐143b und P,P,N,N‐koordinierende Liganden 145. Leider sind die meisten dieser chiralen Ferrocenliganden offenbar nur in dieser speziellen Reaktion wirksam, und in nur sehr wenigen Fällen wurde über eine Anwendung auf anspruchsvollere Substrate berichtet.…”