NUCLEOPHILIC ADDITIONS TO THE CHIRAL RHENIUM ALKENE COMPLEXES [RE(ETA(5)-C5H5)(NO)(PPH(3))(H2C=CHR)]BF4 (R=H, ME, CH(2)CH(2)ME, PH OR CH(2)PH) - REGIO-SELECTIVITIES, DEASTEREO-SELECTIVITIES AND ENANTIO-SELECTIVITIES

Reactions of alkene complexes [Re(eta(5)-C5H5)(NO)(PPh(3))(H2C=CHR)]BF 4 1 (R=H a, Me b, CH(2)CH(2)Me c, Ph d or CH(2)Ph e) and LiCuMe(2) in tetrahydrofuran (thf) at -80 degrees C gave the primary, beta-branched alkyl complexes [Re(eta(5)-C5H5)(NO)(PPh(3))(CH(2)CHMeR)] 2 (79-99%). No secondary, alkyl complexes derived from additions to the unsubstit uted = CH2, termini were detected. Product diastereomer and enantiomer ratios matched those of the reactants. Thus, the additions are regios pecific, diastereospecific and enantiospecific. A chemical correlation involving [Re(eta(5)-C5H5)(NO)(PPh(3)){CH2CH(CD3)Me}] and a crystal s tructure determination [(SR,RS)-2e0.5C(6)H(14)] show that attack occur s on the C = C face anti to the rhenium. Reactions of 1a or 1b (in thf ) with NaOMe-MeOH gave predominantly the 2-methoxyalkyl complexes [Re( eta(5)-C5H5)(NO)(PPh(3)){CH2-CH(OMe)R}] (R=H 4a or Me 4b) (92-97%). An alogous reactions of 1c or 1d gave 81-77:19-23 mixtures of 4c or 4d an d the alkenyl complexes (E)-[Re(eta(5)-C5H5)(NO)(PPh(3))(CH=CHR)](85-7 1%). A similar reaction of 1e gave mainly the allyl complex [Re eta(5) -C5H5)(NO)(PPh(3))(CH2CH=CHPh)].