Alpha-amino acids with metallocenyl side chains

A straightforward method for the synthesis of enantiomerically pure bis(valine)metallocenes is presented. Derivatives of lithium cyclopentadienylvaline 1a, b were obtained by addition of the (R)- or (S)-Schöllkopf reagents to 6,6-dimethylfulvene as single enantiomers and gave with FeCl2 or [RuCl2(dmso)4] the chiral metallocenes [Fe[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2] (2a, b) and [Ru[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2] (3a, b). Complex 2b was hydrolyzed to the ferrocenylene-bis(valine-methylester) [[Fe[C5H4-CMe2-CH(NH3+)COOMe]2]2+(Cl-)2] (7) without racemization. Complex 7 could be used as ligand and was treated with [[Cp*IrCl2]2] to afford [Fe[C5H4-CMe2-CH(COOMe)(NH2-IrCp*Cl2)]2] (10). The reactions of 1 with CoCl2, [Re(CO)5Br], [[(cod)RhCl2]2] (cod= 1,5-cyclooctadiene) or [Cp*MCl3] (M= Ti, Zr) gave the cyclopentadienyl complexes [[Co[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2]+ I-] (11) and [Re[C5H4-CMe2-[C4H2N2(OMe)2iPr]](CO)3] (13), [(C8H12)Rh[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (14). [[Rh[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]I]2(mu-I)2] (15), [Cp*Cl2Ti-[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (16), and [Cp*Cl2Zr[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (17), with chiral valine derivatives as substituents on the cyclopentadienyl ring and with excellent diastereoselectivities. Also the Seebach reagent (Boc-BMI) or O'Donnell reagent could be added to 6,6-dimethylfulvene to give the lithium cyclopentadienides Li[C5H4-CMe2-[C3H2(tBu)(N-Boc)(NMe)O]] (18) and Li[C5H4-CMe2-CH(NCPh2)(COOEt)] (21), which formed the ferrocene derivatives [Fe[C5H4-CMe2-[C3H2(tBu)(N-Boc)(NMe)O]]2] (19) and [Fe[C5H4-CMe2-CH(NCPh2)(COOEt)]2] (22). The stable cobaltocinium cation in 11 and the complex 19 could be hydrolyzed to the metallocenes 12 and [Fe(C5H4-CMe2-CH(NH3+)(COO-)]2] (20) with two valines in the 1,1'-position. The structures of 2a, b, 11, 15, and 16 were determined by X-ray diffraction and confirm the diastereomeric purity of the compounds.