Reaction of [IrCp*Cl2]2 with ferrocenylimines (Fc=NAr, Ar = Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp*,RIr*. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality via an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.
Phytochemical investigations of the stems of Tinospora crispa led to the isolation of one new aporphine alkaloid, N-formylasimilobine 2-O-β-D-glucopyranoside (1), along with six known alkaloids, N-formylasimilobine 2-O-β-Dglucopyranosyl-(1→2)-β-D-glucopyranoside (2) (tinoscorside A), N-formylanonaine (3), N-formyldehydroanonaine (4), N-formylnornuciferine (5), N-demethyl-N-formyldehydronornuciferine (6), magnoflorine (7), paprazine (8), N-transferuloyltyramine (9), and cytidine (10). The structure of new compound 1 was deduced on the basis of spectroscopic data.
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