Triethylamine → HCID 12069395, compound

Participants

Reaction Steps

The above procedure was followed to react 250 mg (1.634 mmol) of 3-cyano-5-methylhex-3-enoic acid with hydrogen (50 psi) in the presence of 8 mg (0.01634 mmol) of [(S,S)-Et-BPE]Rh(COD)+BF4− and 0.023 mL (0.1634 mmol; 0.1 eq) of triethylamine in 5 mL of methanol at 24° C. for 40 hours. The reaction mixture was filtered, the solvent was removed by evaporation, and the product was shown by proton NMR to be 71% (S)-3-cyano-5-methylhexanoic acid with 84% e.e. for the S-enantiomer. C. The above procedure was repeated, except that no base was added to the reaction mixture. The product was shown by proton NMR to be 26%, (S)-3-cyano-5-methylhexanoic acid having 91% e.e. for the S-enantiomer. D. The above procedure was followed to react 200 mg (1.307 mmol) of 3-cyano-5-methylhex-3-enoic acid with hydrogen (50 psi, 100 hours) in the presence of 10 mg (0.01307 mmol) of [(S,S)-Et-DuPHOS]Rh(COD)+BF4−. The product was shown by proton NMR to be 82% (S)-3-cyano-5-methylhexanoic acid having 56% e.e. for the S-enantiomer. E. The procedure of Example 5D was repeated, except that 0.1 eq. (0.02 mL, 0.1307 mmol) of triethylamine was added to the reactive mixture. The reaction was stopped after 16 hours, and the product was shown to be 86% (S)-3-cyano-5-methylhexanoic acid with 68% e.e. for the S-enantiomer. F. The procedure of Example 5E was repeated, except that 1 eq. (0.18 mL, 1.307 mmol) of triethylamine was added to the reaction mixture, and the reaction was stopped at 16 hours. The product was shown by proton NMR to be 92% converted to (S)-3-cyano-5-methylhexanoic acid having 56% e.e. for the S-enantiomer. G. By following the general procedures from above, 250 mg (1.634 mmol) of 3-cyano-5-methylhex-3-enoic acid was reacted with hydrogen (50 psi, 16 hours. 24° C.) in the presence of 12 mg (0.01634 mmol) of [(R,R)-DIPAMP]Rh(COD)+BF4− in methanol (10 mL) to provide 51% of 3-cyano-5-methylhexanoic acid having 72% e.e. for the R-enantiomer.

Provenance & Evidence