Isoquinolines octahydro

Among the amines that have been resolved with (-)-DAG are a-phenylethylamine (a-methylbenzenemethanamine),s [R-(R, R )]-2-amino-l-(4-nitrophenyl)-l, 3-propanediol,61,2,3,4,5,6,7,8-octahydro-l-(4-methoxyphenylmethyl)isoquinoline, 3-methoxymorphinan, 1,2,3,4-tetrahydro-7-methoxy-4-phenylisoquinoline, 3-hydroxy-A7-methyl-... 

The intramolecular formal [3+3] cycloaddition reaction of l- [l-phenyl-2-(4-oxobut-2-enyloxy)ethyl]amino cyclo-hexen-3-one at 150°C in the presence of piperidinium acetate afforded /ra 3--l,4a-77-l-phenyl-l,2,4,4a,7,8,9,10-octahydro[l,4]oxazino[4,3- ]quinolin-7-one <2002JA10435>. At 85°C, the 6-(l-piperidnyl)-l,2,4,4a,5,6,7,8,9,10-dec-ahydro derivative formed, which could be converted into the l,2,4,4a,7,8,9,10-octahydro derivative by heating at 150 °C. Cyclization of iV-[(2-butyl-2-oxoethoxy)acetyl]-3,4-dimethoxyphenylethylamine on the action of TFA gave llb-butyl-1,3,4,6,7,1 lb-hexahydro[l,4]oxazino[3,4- ]isoquinolin-4-one <1997JOC2080>. 

The above base is catalytically hydrogenated (platinum oxide seems to work the best) to 1-(p-methoxybenzyl)-2-methyl-l,2,3,4,5,6,7,8-octahydro-isoquinoline. This is separated from the... 

Synthesis The analgesic activity of racemorphan is due to the (-) isomer, levorphanol, which is obtained by resolving the racemate with (+)-D-tartaric acid. Resolution can also be carried out on the intermediate 1-(4-Methoxy-benzyl)-1,2,3,4,5,6,7,8-octahydro-isoquinoline 6 prior to N-methylation (Grewe 1946, Schnider and Hellerbach, 1950, Schnider and Griissner, 1951, Ehrhart and Ruschig 1972, Kleemann et al. 1999). 

R = OMe, R1 = H), whereas reduction with sodium borohydride in methanol in the presence of sodium hydroxide gave 10,11-dimethoxy-l,2,3,4,5,6,7,8-octahydro-2,6-benzodiazocine (92) (59YZ1014). Treatment of 1,3,4,1 lb-tetrahydro-2//-pyrimido[2,l-a]isoquinoline with LAH in boil-... 

Ethyl 2-(cyanomethylene)cyclohexanecarboxylate (379) and /V-methyl-propylenediamine in o-dichlorobenzene at 170-180°C for 24 h yielded 1-methyl-l,2,3,4,7,8,9,10-octahydro-6//-pyrimido[l,2-b]isoquinolin-6-one (380) (78GEP2731982 79YZ880 81BRP1588166,81USP4284778). 

Reaction of l-mercapto-4-cyano-5,6,7,8-tetrahydroisoquinolin-3(2//)-one with 3-bromopropionic acid in boiling ethanol in the presence of sodium acetate gave octahydro[l,3]thiazino[2,3-a]isoquinoline-4,6-dione (216) (89PS203). 

The effects of enantiomorphs of TAN-67 (2-methyl-4aa-(3-hydroxy-phenyl)-l,2,3,4,4a,5,12,12aa-octahydro-quinolino[2,3,3-g]isoquinoline), (-) TAN-67 and ( + )TAN-67 on antinociceptive response has been recently investigated. (-)TAN-67 produces a significant antinociceptive response when given ITH. [43]. The antinociceptive response induced by (-)TAN-67 can be blocked by pretreatment with delta but not by mu or kappa opioid receptor... 

Both analytical LC and quantitative TLC have been used successfully in the separation of all the regioisomers ([2,3- ] vs. [2,3-h]) and stereoisomers (trans-fused vs. cw-fused) of octahydro, pyrrolo-fused isoquinolines <84JOC5109>. 

The conjugate addition of dimethylcopperlithium to the 2-methyl-6-keto-octahydro-isoquinoline (14) leads uniquely to the 2,10-dimethyl-6-keto-decahydroisoquinoline (15) with as ring junction.7... 

For a number of years prior to Evans revelations, Rapoport had been involved in the development of a general methodology for the synthesis of several morphine structural analogues. These included both cis and trans 4a-aryldecahydroisoquinolines 127,65 octahydro-lH-benzofuro-[3,2-e]-isoquinolines 128,66 and novel octahydro-lH-[l]-benzopyrano-[4,3,2-e,f]-isoquinolines 129 67... 

In the course of an investigation on the synthesis of eizapolycycles containing an octahydro-isoquinoline moiety the following reactions were carried out ... 

The raeemie mixture dl) of l-(p-hydroxybenzyl)-2-methyl-1,2,3,4,5,6,7,8-octahydro-isoquinoline may be obtained exactly in the same manner as described for levorphanol tartrate (in 1 above). This is now resolved to get the J-enantiomorph and then treated with phenyltrimethyl ammonium hydroxide to cause methylation and yield the dextromethorphan base. Treatment of the base with appropriate amount of hydrobromide gives the eorresponding hydrobromide. 

Moos WH, Gless RD, Rapoport H (1983) Codeine analogs - synthesis of 4a-aryldecahy-droisoquinolines containing nitrogen ring functionality and of octahydro-1 h-indeno[l,2,3-ef]isoquinolines - a total synthesis of codeine. J Org Chem 48 227-238 Toth JE, Euchs PL (1987) Syntheses via vinyl sulfones. 21. Total synthesis of dl-morphine. 

Among the amines that have been resolved with (-)-DAG are a-phenylethylamine (a-methylbenzenemethanamine), [R-(R, R )]-2-amino-l-(4-nitrophenyl)-l,3-propanediol, 1,2,3,4,5,6,7,8-octahydro-l-(4-methoxyphenylmethyl)isoquinoline, 3-methoxymorphinan, 1,2,3,4-tetrahydro-7-methoxy-4-phenylisoquinoline, 3-hydroxy-i 7-methyl-morphinan, l,2,3,4-tetrahydro-6,7-dimethoxy-l-[3,4-(methylenedi-oxy)phenyl]isoquinoline, l,2,3,4-tetrahydro-6,7-dimethoxy-l-(3,4,5-tri-methoxyphenyl)isoquinoline, 2-[4-(phenylmethoxy)phenyl]-2-(3,4-di-methoxyphenyl)ethanamine, A-norlaudanosine (tetrahydropapaver-ine), and l,2,3,4-tetrahydro-6,7-dimethoxy-l-[3-methoxy-4- phenyl-methoxy)phenyl]isoquinoline. 

Asymmetric total synthesis of (—)-octahydro-l f-benzofuro[3,2- ]isoquinoline 149, a partial structure of morphine, a potent analgesic alkaloid, was accomplished using the ATH protocol (Scheme 30.28). The ketone 147... 

Hsin L-W, Chen C-W, Chang L-T. Asymmetric total synthesis of( ) octahydro-lHbenzojuro[3,2-e]isoquinoline, a partial structure of morphine. J. Chin. Chem. Soc. 2005 52 (2) 339 346. 

---