Asymmetrische reaktionen XIII die absolute konfiguration des alkaloids 1S,5S-(−)-argemonin und der 1S,5S-(+)-troegerschen base

Synthesis, Resolution, and Absolute Configuration of Difunctionalized Tröger's Base Derivatives

“…[6] The absolute configuration of 1 was first investigated in 1966, on the basis of comparative optical rotational dispersion (ORD) curves of the two pure enantiomers and (À)-argemonine, an alkaloid with a related structure: the (+)-enantiomer of 1 was attributed the (5S,11S) configuration. [7] Later work on the basis of circular dichroism studies, by using the exciton chirality method, [8] came to the opposite conclusion; this, however, proved to be incorrect due to an erroneous assignment of the direction of polarization of the considered transitions. This assignment was believed to be true until 1991, when Wilen et al finally proved by X-ray diffraction on a diastereomeric salt of (+)-1 and (À)-1,1'-binaphthyl phosphoric acid that the initial assignment made in 1966 was correct.…”

The Pavine and Isopavine Alkaloids

“…153.5-155° (5) 155-156°(Et20) (6) 155.5-156.6°(EtOH) (7) (hydrate) 125-135° (8) [ ]24 : -187.93°(c= 1.01, CHC13) (4) Ia]D: -202°(CHC13)(3) [a}25D: -203°(c=3.31, CHC13) (5) [a]21D: -208°±3°(c=0.5, CHC13) (9) [a]27D: -209°(c = 0.5, CHC13) (8) [a]24D: -214.22°(c= 1.01, EtOH)(4,10) [a]20D: -226°(c=0. 20) Absolute Configuration: (18,20,21,22) X-RAY: Methiodide (23) SOURCES: PAPAVERACEAE: Argemone gracilenta Greene (5), A. hispida Gray (4, 8, 14), A. munita Dur. and Hilg.…”

“…( -)-amurensine, (-)-amurensinine ( -)-amurensine (-)-amurensinine ( -)-amurensine, (-)-amurensinine ( -)-amurensine, (-)-amurensinine ( -)-amurensine, (-)-amurensinine (-)-amurensine, (-)-amurensinine ( -)-reframidine, (-)-reframine, (-)-reframoline, (-)remrefine ( -)-bisnorargemonine, ( -)-norargemonine, ( -)thalisopavine ( -)-thalidicine, ( -)-thalidine ( -)-argemonine, (-)-argemonine N-metho salt, ( -)eschscholtzidine, (-)-eschscholtzidine N-metho salt, (-)-isonorargemonine, (-)-platycerine (-)-argemonine, (-)-2,3 -methylenedioxy-4,8,9trimethoxypavinane Alphabetical List of Pavine Alkaloids (-)-Argemonine (1) (+ )-Argemonine (2) (-)-Argemonine N-metho salt (3) (-)-Argemonine N-oxide (4) (-)-Bisnorargemonine (7) (-)-Californidine (15) (-)-Cary achine (11) (±)-Caryachine (12) (-)-Caryachine N-metho salt (13) (-)-Eschscholtzidine (8) (+ )-Eschscholtzidine (9) (-)-Eschscholtzidine N-metho salt (10) (-)-Eschscholtzine ( 14) (-)-2-Hydroxy-3,8-dimethoxypavinane (20) (-)-Isonorargemonine (6) (-)-2,3-Methylenedioxy-4,8,9trimethoxypavinane (21) (-)-Munitagine (19) (-)-0-Methylplatycerine (16) (-)-Norargemonine (5) (-)-Platycerine (17) (-)-Platycerine N-metho salt (18) Alphabetical List of Isopavine Alkaloids (-)-Amurensine (29) (-)-Amurensinine (26) (-)-0-Methylthalisopavine (22) (-)-Reframidine (31) (-)-Reframine (27) (-)-Reframoline (30) (-)-Remrefine (28) (-)-Thalidicine (24) (-)-Thalidine (25) (-)-Thalisopavine (23) ACKNOWLEDGMENT This compilation was carried out in conjunction with research supported by grant no. CA-11450 awarded by the National Cancer Insitute, National Institutes of Health, USPHS.…”

Synthesis and configuration determination of enantiopure 4,10-bis-ortho-substituted Tröger’s base derivatives

“…Historically, the absolute configuration of (+)-1 was wrongly assigned to 5R,11R by the circular dichroism (CD) and optical rotatory dispersion spectra. [30][31][32] Subsequently, X-ray diffraction (XRD) analysis, 6 vibrational CD and optical rotatory calculation, [33][34][35] and DFT computational studies 36 finally revised the absolute configuration of (+)-1 to be 5S,11S. Firstly,…”