SYNTHESIS, STRUCTURE, AND REACTIVITY OF N-INDOLYL COMPLEXES OF THE CHIRAL RHENIUM LEWIS-ACID [(ETA-5-C5H5)RE(NO)(PPH3)]+ - DIASTEREOSELECTIVE ELECTROPHILIC ADDITIONS Academic Article uri icon

abstract

  • Reactions of the triflate complex (5-C5H5)Re(NO)PPh3)OTf) (3) and indolide salts K(NCHC(R)CCCHCHCHCH) give the N-indolyl complexes (5-C5H5)Re(NO)(PPh3)-(NCHC(R)CCCHCHCHCH) (2, R = H/CH3/C2H5 (a/b/c); 7159% after crystallization). Reactions of 2a,b and HOTf give the indolenine complexes [(5-C5H5)Re(NO)(PPh3)- (NCHCH(R)CCCHCHCHCH)]+ TfO- (4+TfO-; a, 93%; b, 77%, (8692):(14-8) SR,RS/SS,RR Re,C diastereomers). Reaction of 2b and CH3OTf gives [(5-C5H5)Re(NO)(PPh3)-(N=CHC(CH3)2CCCHCHCHCH)]+TfO- (5+TfO-, 96%). Reactions of 2b and C2H5OTf, and 2c and CH3OTf, give (5-C5H5)Re(NO)(PPh3)NCHC(CH3)(C2H5)CCCHCHCHCH)]+ TfO- (6+TfO-, 9296%; 65:35, 17:83 SS,RR/SR,RS, respectively). Reaction of 2b and [(5- C5H5)Re(NO)(PPh3)(IC2H5)]+BF4- gives 6+BF4- (93%, 91:9 SS,RR/SR,RS) and (5-C5H5)Re-(NO)(PPh3)(I) (84%). Reactions of 5+TfO- and CH3MgCl or LiB(C2H5)3H (THF, -80 C) give addition products (5-C5H5)Re(NO)(PPh3)(NCH(R)C(CH3)2CCCHCHCHCH) (R CH3 (95:5 SS,RR/SR,RS), H). The latter and HOTf yield indoline complex [(5-C5H5)Re(NO)- (PPh3)(HNCH2C(CH3)2CCCHCHCHCH)]+,TfO- (9+TfO-, 85%), which when treated with CNCH2Ts (60 C, CHCl3) gives 3,3-dimethylindoline (81%) and [(5-C5H5)Re(NO)- (PPh3)(CNCH2Ts)]+TfO- (14+TfO-, 77%). Reaction of 3 and CNCH2Ts also gives 14+TfO- (94%), which is reduced by BH3THF (THF, reflux) to (5-C5H5)Re(NO)(PPh3)(CH3) (60%). The crystal structure of 2c, reactions of nonracemic compounds, and rationales for the preceding configurational assignments are also reported. 1994, American Chemical Society. All rights reserved.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • JOHNSON, T. J., ARIF, A. M., & GLADYSZ, J. A.

citation count

  • 25

complete list of authors

  • JOHNSON, TJ||ARIF, AM||GLADYSZ, JA

publication date

  • August 1994