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p- Phenylethylamines and the lsoquinol ine Alkaloids
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K. W. Bentley Marrview, Tillybirloch, Midmar, Aberdeenshire At35 I 7PS Reviewing the literature published between July 1990 and June 1991 (Continuing the coverage of literature in Natural Product Reports, 1991, Vol. 8, p. 339)
1 2 3 4 5 6 7 8 9 10 11 12 13
14 15 16 17 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 17.9 18 19 20 21 22 22.1 22.2 22.3 23 24
p-Phenylethy lamines Isoquinolines Benzylisoquinolines Bisbenzylisoquinolines Cularines Pavines and Isopavines Benzopyrrocolines Berberines and Tetrahydroberberines Secoberberines Protopines Phthalide-isoquinolines Spirobenzylisoquinolines Rhoeadines Other Modified Berberines Emetine and Related Alkaloids Benzophenanthridines Aporphinoid Alkaloids Proaporphines Aporphines Dimeric Aporphines Aporphine-Benzylisoquinoline Dimers Oxoaporphines Dioxoaporphines Phenanthrenes Aristolochic Acids and Aristolactams 0x0-isoaporphines Morphine Alkaloids Phenethylisoquinolines Homoaporphines Colchicine and its Analogues Erytlzrina and Related Alkaloids Erjithrinu A1kaloids Homoerythrina Alkaloids Cephalotaxine and its Analogues Other Alkaloids References
(3)
I /IPhenylet hylamines Several new bishordeninyl terpene alkaloids have been isolated from Zanthoxylum species. Z . chiriquinurn has yielded the known alfileramine (1, R1 = H, R2 = R3 = Me) and the new bases 0-methylalfileramine (1, R' = R2 = R3 = Me), isoalfileramine (2, R = Me) and culantraramine (3, R = Me)' and Z . coriaceum has yielded N-demethylalfileramine (1, R' = R2 = H, R3 = Me), N'-demethylalfileramine ( I , R' = R3 = H, R2 = Me), N,N-didemethylalfileramine (1, R' = R2 = R3 = H), N , N didemethylisoalfileramine (2, R = Me) and N,N-didemethylculantraramine (3, R = H).2 In addition the new alkaloid 4-(2N-methyltyraminy1)-(2)- 172-epoxy-2-methylbut-3-ene (4) has been isolated from Z . coriaceurn.2 Methods for the estimation of ephedrine in body fluid^^.^ and in plant material5 have been described, as have syntheses of N-p-nitrobenzoylephedrine6 and other derivatives of the alkaloid,' the effects of ephedrine on seizures induced by theophylline,8 the anorexic effects of n~rephedrine,~ and the biological oxidation and N-demethylation of methylephedrine. l o
"
O
NHMe 9
(4)
2 lsoquinolines Cotarnine has been isolated from Papaver pseudo-orientale, l1 and 8-hydroxy-7-methoxy-2-methyl172,3,4-tetrahydroisoquinoline, previously known only by synthesis, has been isolated as a new alkaloid from Ceratocapnos palaestinus.12 A novel complex derivative of two units of tetrahydroisoquinoline, obtained from a marine ascidian, is described in Section 23. The lH and 13CNMR spectra of hydrocotarnine, heliamine, and 0-methylcorypalline have been studied in detail.I3 (-)Salsoline has been synthesized by a previously reported route'4 and cotarnine iodide has been synthesized by the BischlerNapieralsky15 and Pommeranz-Frisch16 routes. (S)-Crypto365
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%
366
NATURAL PRODUCT REPORTS, 1992
Meo
Me0
Me0 Me0
Me0
0
Me0 ~
R' 0
3
0
R
3
OR2 Published on 01 January 1992. Downloaded by University of Illinois at Chicago on 22/10/2014 21:48:23.
(5)
OMe OMe
OMe OMe
OMe OMe
I
I
Meo RwN::;2p Me
Me0
OMe OMe
OMe OMe
Me
Me0
Me0 OMe
OMe Me
styline I ( 5 , R' = H, R2R3= CH,) has been prepared by the reaction of the iminium salt (6) with the appropriate Grignard reagent, followed by reductive removal of the benzylic group attached to the nitrogen atom and subsequent N-methy1ation.l' It has also been prepared by the stereospecific reduction of the salt (7, R' = H, R2R3= CH,) by Itsumo's reagent and by Maskerh's reagent, and its analogues (S)-cryptostyline I1 ( 5 , R' = H, R2 = R3= Me) and (S)-cryptostyline I11 (5, R1= OMe, R2 = R3= Me) have been prepared by similar reductions of the corresponding salts (6).lS In the 5-naphthylisoquinoline group of alkaloids, 0-methylancistrocladine (1 3 ) and its rotational isomer 0-methylhamatine have been synthesized from the oxazole derivative (8), which, with the Grignard reagent (9), gave the phenylnaphthalene (1 0) which was transformed successively into (10, R = CO,Me), (10, R = CH,OH), and (10, R = Me). Hydrolysis of the last of these to the aldehyde (11) was followed by condensation with nitroethane and reduction to the amine (12). The two enantiomers of this amine were separated as amides of the optically pure 2-hydroxy-4-phenylbutyric acid. BischlerNapieralsky cyclization of the N-acetyl derivatives of (1 2), followed by reduction, then gave the isomeric alka10ids.l~The 7-naphthylisoquinoline (1 5, R = Me) has been synthesized by internal coupling of the ester (14), followed by hydrolysis of the lactone, 0-methylation, esterification, reduction of the ester to the primary alcohol, conversion of CH,OH into CH,, and final N-debenzylation. 2o A similar synthesis of triphyophylline ( 1 6), which has been renamed dioncophylline A, has been accomplished.21 It has, however, been noted that the 0-
0
Me
\
0
methylation of this alkaloid gives a base that is different from the ' 0-methyltriphyophylline ' obtained from plant The NMR spectra of ancistrocladidine have been ~ t u d i e d . ' ~
3 Benzyl isoquinoli nes Benzylisoquinoline alkaloids have been isolated from the following plant species, the four marked with asterisks being new alkaloids : Ceratocapnos palaest inus" N-methylcoclaurine, juziphine, and reticuline Corydalis c l a v i ~ u l a t a ~ ~ Crassifoline, crassifoline methine* ( 17), juziphine, leonticine (petaline methine), reticuline, and viguine Fumaria indica2j fumarizine* ( I 8) Papaver somniferum26 papaverine Polyalthia macro pod^^^ coclaurine Roemeria refractaZ8 armepavine, pseudolaudanine" (1 9, R = UMe), roefractine" (19 R = H), and roemacarine Sarcocapnos crass~olia2g crassifoline Siparuna t o n d u ~ i a n a ~ ~ reticuline Zizyp h us vulgar is" coclaurine.
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367
NATURAL PRODUCT REPORTS, 1992-K. W. BENTLEY
MeO%oH Me0
Me0
Published on 01 January 1992. Downloaded by University of Illinois at Chicago on 22/10/2014 21:48:23.
Me0
p- Phenylethylamines and the lsoquinol ine Alkaloids
Published on 01 January 1992. Downloaded by University of Illinois at Chicago on 22/10/2014 21:48:23.
K. W. Bentley Marrview, Tillybirloch, Midmar, Aberdeenshire At35 I 7PS Reviewing the literature published between July 1990 and June 1991 (Continuing the coverage of literature in Natural Product Reports, 1991, Vol. 8, p. 339)
1 2 3 4 5 6 7 8 9 10 11 12 13
14 15 16 17 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 17.9 18 19 20 21 22 22.1 22.2 22.3 23 24
p-Phenylethy lamines Isoquinolines Benzylisoquinolines Bisbenzylisoquinolines Cularines Pavines and Isopavines Benzopyrrocolines Berberines and Tetrahydroberberines Secoberberines Protopines Phthalide-isoquinolines Spirobenzylisoquinolines Rhoeadines Other Modified Berberines Emetine and Related Alkaloids Benzophenanthridines Aporphinoid Alkaloids Proaporphines Aporphines Dimeric Aporphines Aporphine-Benzylisoquinoline Dimers Oxoaporphines Dioxoaporphines Phenanthrenes Aristolochic Acids and Aristolactams 0x0-isoaporphines Morphine Alkaloids Phenethylisoquinolines Homoaporphines Colchicine and its Analogues Erytlzrina and Related Alkaloids Erjithrinu A1kaloids Homoerythrina Alkaloids Cephalotaxine and its Analogues Other Alkaloids References
(3)
I /IPhenylet hylamines Several new bishordeninyl terpene alkaloids have been isolated from Zanthoxylum species. Z . chiriquinurn has yielded the known alfileramine (1, R1 = H, R2 = R3 = Me) and the new bases 0-methylalfileramine (1, R' = R2 = R3 = Me), isoalfileramine (2, R = Me) and culantraramine (3, R = Me)' and Z . coriaceum has yielded N-demethylalfileramine (1, R' = R2 = H, R3 = Me), N'-demethylalfileramine ( I , R' = R3 = H, R2 = Me), N,N-didemethylalfileramine (1, R' = R2 = R3 = H), N , N didemethylisoalfileramine (2, R = Me) and N,N-didemethylculantraramine (3, R = H).2 In addition the new alkaloid 4-(2N-methyltyraminy1)-(2)- 172-epoxy-2-methylbut-3-ene (4) has been isolated from Z . coriaceurn.2 Methods for the estimation of ephedrine in body fluid^^.^ and in plant material5 have been described, as have syntheses of N-p-nitrobenzoylephedrine6 and other derivatives of the alkaloid,' the effects of ephedrine on seizures induced by theophylline,8 the anorexic effects of n~rephedrine,~ and the biological oxidation and N-demethylation of methylephedrine. l o
"
O
NHMe 9
(4)
2 lsoquinolines Cotarnine has been isolated from Papaver pseudo-orientale, l1 and 8-hydroxy-7-methoxy-2-methyl172,3,4-tetrahydroisoquinoline, previously known only by synthesis, has been isolated as a new alkaloid from Ceratocapnos palaestinus.12 A novel complex derivative of two units of tetrahydroisoquinoline, obtained from a marine ascidian, is described in Section 23. The lH and 13CNMR spectra of hydrocotarnine, heliamine, and 0-methylcorypalline have been studied in detail.I3 (-)Salsoline has been synthesized by a previously reported route'4 and cotarnine iodide has been synthesized by the BischlerNapieralsky15 and Pommeranz-Frisch16 routes. (S)-Crypto365
View Article Online
%
366
NATURAL PRODUCT REPORTS, 1992
Meo
Me0
Me0 Me0
Me0
0
Me0 ~
R' 0
3
0
R
3
OR2 Published on 01 January 1992. Downloaded by University of Illinois at Chicago on 22/10/2014 21:48:23.
(5)
OMe OMe
OMe OMe
OMe OMe
I
I
Meo RwN::;2p Me
Me0
OMe OMe
OMe OMe
Me
Me0
Me0 OMe
OMe Me
styline I ( 5 , R' = H, R2R3= CH,) has been prepared by the reaction of the iminium salt (6) with the appropriate Grignard reagent, followed by reductive removal of the benzylic group attached to the nitrogen atom and subsequent N-methy1ation.l' It has also been prepared by the stereospecific reduction of the salt (7, R' = H, R2R3= CH,) by Itsumo's reagent and by Maskerh's reagent, and its analogues (S)-cryptostyline I1 ( 5 , R' = H, R2 = R3= Me) and (S)-cryptostyline I11 (5, R1= OMe, R2 = R3= Me) have been prepared by similar reductions of the corresponding salts (6).lS In the 5-naphthylisoquinoline group of alkaloids, 0-methylancistrocladine (1 3 ) and its rotational isomer 0-methylhamatine have been synthesized from the oxazole derivative (8), which, with the Grignard reagent (9), gave the phenylnaphthalene (1 0) which was transformed successively into (10, R = CO,Me), (10, R = CH,OH), and (10, R = Me). Hydrolysis of the last of these to the aldehyde (11) was followed by condensation with nitroethane and reduction to the amine (12). The two enantiomers of this amine were separated as amides of the optically pure 2-hydroxy-4-phenylbutyric acid. BischlerNapieralsky cyclization of the N-acetyl derivatives of (1 2), followed by reduction, then gave the isomeric alka10ids.l~The 7-naphthylisoquinoline (1 5, R = Me) has been synthesized by internal coupling of the ester (14), followed by hydrolysis of the lactone, 0-methylation, esterification, reduction of the ester to the primary alcohol, conversion of CH,OH into CH,, and final N-debenzylation. 2o A similar synthesis of triphyophylline ( 1 6), which has been renamed dioncophylline A, has been accomplished.21 It has, however, been noted that the 0-
0
Me
\
0
methylation of this alkaloid gives a base that is different from the ' 0-methyltriphyophylline ' obtained from plant The NMR spectra of ancistrocladidine have been ~ t u d i e d . ' ~
3 Benzyl isoquinoli nes Benzylisoquinoline alkaloids have been isolated from the following plant species, the four marked with asterisks being new alkaloids : Ceratocapnos palaest inus" N-methylcoclaurine, juziphine, and reticuline Corydalis c l a v i ~ u l a t a ~ ~ Crassifoline, crassifoline methine* ( 17), juziphine, leonticine (petaline methine), reticuline, and viguine Fumaria indica2j fumarizine* ( I 8) Papaver somniferum26 papaverine Polyalthia macro pod^^^ coclaurine Roemeria refractaZ8 armepavine, pseudolaudanine" (1 9, R = UMe), roefractine" (19 R = H), and roemacarine Sarcocapnos crass~olia2g crassifoline Siparuna t o n d u ~ i a n a ~ ~ reticuline Zizyp h us vulgar is" coclaurine.
View Article Online
367
NATURAL PRODUCT REPORTS, 1992-K. W. BENTLEY
MeO%oH Me0
Me0
Published on 01 January 1992. Downloaded by University of Illinois at Chicago on 22/10/2014 21:48:23.
Me0
