Deprotonation and anionic rearrangements of organometallic compounds. 5. Kinetic vs. thermodynamic deprotonation in reactions of cyclopentadienylrhenium acyl and alkyl complexes with strong bases Academic Article uri icon


  • Reaction of 5-C5H5)Re(NO)(PPh3)(COR) (la, R = CH3; lb, R = CH2C6H5; lc, R = C6H5; Id, R = H) with Li+-N(CH(CH3)2)2(LDA; THF, -78 C) and then CH3I gives (5-C5H4COR)Re(NO)(PPh3)(CH3) (2a-d, 50-78%). Deuterium-labeling experiments indicate that 1 is initially deprotonated to (5-C5H4Li)Re(NO)(PPh3)(COR) (3), and 31P NMR shows a subsequent rapid rearrangement (3a: <3 min, -95 C) to Li+ [(5-C5H4COR)Re(NO)(PPh3)]-(4). Crossover experiments show 3 4 to be intramolecular. Reaction of (5-C5H5)Re(NO)(PPh3)(CH2C6H5) with n-BuLi/TMEDA (-78 C, 5 min) gives (5-C5H4Li)Re(NO)(PPh3)(CH2C6H5) (6), which does not rearrange upon warming and yields (5-C, H4CH3)Re(NO)(PPh3)(CH2C6H5) (7, 74%) upon addition of CH3I. When (+)-(S)-(5-C5H5)Re(NO)(PPh3)(CH3) ((+)-(S)-8, >98% ee) is treated with /n-BuLi/TMEDA and then (RCO)2O (R = CH3, C6H5CH2, C6H5), (-)(S)2a, (-)(S)2b, and (-)(S)-2c, all 98% ee, are obtained. Experiments with optically active 1 then show that 3a 4a proceeds with >90% retention of configuration at rhenium and that 3b 4b and 3c 4c proceed with lesser degrees of retention and inversion, respectively. Pentamethylcyclopentadienyl complexes (5-C5Me5)Re(NO)(PPh3)(COCH2R) (10a, R = H; 10b, R = C6H5) and n-BuLi react to give enolates Li+(5-C5Me5)Re(NO)(PPh3)(C(O-)==CHR), which yield (5-C5Me5)Re(NO)(PPh3)(COCH(R)CH3) (72-82%) when treated with CH3I. When lb is treated with the weaker base Li+-N(Si(CH3)3)2, E-enolate Li+(5-C5H5)-Re(NO)(PPh3)(C(O-)=CHC6H5(17) forms and gives (SR, RS)-(5-C5H5)Re(NO)(PPh3)(COCH(C6H5)CH3) ((SR, RS)- 16) with 96% diastereoselectivity when treated with CH3I. The factors controlling the stereoselectivity and site of deprotonation in these reactions, and the relationship of 3 4 to anionic organic rearrangements, are discussed. 1986, American Chemical Society. All rights reserved.

published proceedings

  • Journal of the American Chemical Society

author list (cited authors)

  • Heah, P. C., Patton, A. T., & Gladysz, J. A.

citation count

  • 49

complete list of authors

  • Heah, Poh Choo||Patton, Alan T||Gladysz, JA

publication date

  • March 1986