Diastereomeric Reissert compounds of isoquinoline and 6,7-dimethoxy-3,4-dihydroisoquinoline in stereoselective synthesis.
Chiral acid chlorides were reacted with isoquinoline and 6,7-dimethoxy-3,4-dihydroisoquinoline to form diastereomeric Reissert compounds 8-11 and 18-21, respectively. The best diastereoselectivity (80:20) was achieved in formation of the 9-phenylmenthyl derivative 20. The diastereomers of 2-l-menthoxycarbonyl-1,2-dihydroisoquinaldonitriles (S)-8/(R)-8), formed in equal amounts, were inseparable. However, the individual diastereomers of 2-cholesteryloxycarbonyl-1,2-dihydroisoquinaldonitriles ((R)-11 and (S)-11) and the 2-l-menthoxycarbonyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinaldonitriles ((S)-19/(R)-19)) were each readily purified. (S)-8/(R)-8 (1:1) via the corresponding anions (NaH, -40 degrees C, DMF) with pivaldehyde yielded in 82:18 predominance the S-diastereomer of 1-isoquinolyl tert-butyl carbinyl l-menthyl carbonate ((S)-12), which was obtained in pure form by a single recrystallization; hydrolysis produced 99% pure S-(-)-1-isoquinolyl tert-butyl carbinol [(S)-16]. Reactions of the anions of diastereomeric Reissert compounds, either as mixtures or pure single species, with aromatic aldehydes and alkyl halides proceeded with at best modest selectivity (diastereomeric ratios up to 66:34 and 72:28, respectively). Therefore, it is concluded that the Reissert anions are either planar or rapidly inverting tetrahedral structures.
Gibson
Harry W
HW
Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA. hwgibson@vt.edu
Berg
Michael A G
MA
Dickson
Jennifer Clifton
JC
Lecavalier
Pierre R
PR
Wang
Hong
H
Merola
Joseph S
JS
D000447:Aldehydes / Q000737:chemistry; D000478:Alkylation; D002851:Chromatography, High Pressure Liquid; D007546:Isoquinolines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism
D000447:Aldehydes; D007546:Isoquinolines; C001058:pivaldehyde