Synthetic photochemistry. Synthesis of (±)oliveroline and (±)ushinsunine

Kessar, S. V.; Gupta, Y. P.; Yadav, Vikas; Narula, M.

doi:10.1016/s0040-4039(00)78675-8

Cited by 16 publications

(17 citation statements)

References 8 publications

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“…fur C,,H,,BrNO,(446,34): C 59,20,H 5,42,N 3,14;gef. : C 59,49,H 5,41,N 3.12. 2.13. u -(1-(2-Brom-cc-h~droxy-3.4-dimeth~xybenzJ;I/-I.2.3,4-tetrahydro-6,7-lmethylendio,~.v) (l,9), 204 (1,6), 176 ( 4 3 3 , 57 (99,6).…”

Section: U-[i -(2-brom-a-hydroxy-34-dimethoxybenzyl) -I 234-tementioning

confidence: 99%

“…Unseres Wissens gibt es bisher nur eine Totalsynthese, die zu einem (1:l)-Gemisch der racemischen Formen von Ushinsunin und des Epimeren (Oliverolin) fiihrte [41]. Unsere diastereoisomerenreinen Aminoalkohole uund I-14c (aus 2 und 2-Brombenzaldehyd) wurden nun in zwei Schritten nach dem in der nicht stereoselektiven Synthese [41] verwendeten Verfahren in die pentacyclischen Tetrahydroisochinolin-Alkaloide ubergefuhrt (Sckema 4 ) : zunachst wurde durch Kochen rnit methanolischem Formalin und Reduktion rnit NaBH,CN bei pH 3 [4446] am N-Atom methyliert (+20) und dann durch Belichten [47] [48] in 3% wassr. HC1-Losung mit massiger Ausbeute cyclisiert.…”

Section: )unclassified

“…H); 4,45 (q, J = 7,5,CH,); 3,93 (s, CH,O); 3,85 (s, CH,O); 1,98 (I, J = 6,6,CH,). MS: 238 (21,9,M"), 209 (loo), 193 (56,9), 165 (48,7), 149 (14,6), 135 (12,2), 132 (15,6), 107 (18,5), 77 (21,4), 28 (45,9) 22; 134,13; 128,66; 128,28; 126,86; 126,03; 78,57; 58,64; 41,84; 39,ll; 29,l 1; 28,42; 26,96; 10,90. 139,08; 134.24; 134.00; 129,29; 128,79; 128.50; 127,14; 126,36; 126,17; 77,54 (d); 58,45 ( d ) ; 41 (20 MHz, CDCI,): 178,87;137,42;133,81;133,17;128,47;127,76;126,73;125,95;115,39;78,15;85,27;41,75;38,79;2833;28,15.…”

Section: ( Tert-buiy~)-[i234-terrahydro-67-(dimethoxy) Isochinoliunclassified

“…: C 74,56, H 8.58, N 5,03. 2.5. u 45;137,OO;134,02;133,49;130,50;129,Ol;128,79;128,56;128,lO;127,48;127,07;78,46;59,06;42,27;39,10;29,14;28,36 9 arom. H); 5,98 (d, J = 3, CHN); 5,32 (d, J = 3, CHOH); 5,24 (s, OH); 3,96338 (1 H), 2,94-2,23 (3 H) (2m, CH2CH2); 1,25 (s, t-Bu).…”

Section: ( Tert-buiy~)-[i234-terrahydro-67-(dimethoxy) Isochinoliunclassified

“…H); 5,2 (dt, J = 10,3, CH-0); 4,2 (d, J = 3, CHN); 3,33-2,47 (m, ArCH2CH2); 2,O-1,27 (m, CH3CH2, NH); 1,20 (s, t-Bu). ',C-NMR (20 MHz,CDCI,): 178,12;136,15;135,lO;129,25;126,47;126.17;125,86;125,73;79,ll;58,lO;41,94;39,Ol;30,18;27,28;21,79;10,48. MS: 274 ( < 1, M+' -I), 133 (1 l), 132 (loo), 130 (6), 57 (5). Anal.…”

Section: 17 U-( Tert-bu~yll-[1234-tetralzydro-l-(a-h~droxy-cc-mrunclassified

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Diasteroselektive Hydroxyalkylierungen in 1‐Stellung von Tetrahydroisochinolinen und Synthese von Aporphin‐, Protoberberin‐ und Phthalid‐Alkaloider

Seebàch¹,

Isabelle²,

Max³

1987

Helvetica Chimica Acta

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Unsubstituted and 6,7-dialkoxy-N-pivaloyl-tetrahydroisoqu~nolines 1-3 are converted to l-bromomagnesium derivatives by sequential treatment with 1-BuLi (-75"/THF) and MgBrz.0Et2. Addition of the metalated tetrahydroisoquinolines to aliphatic or aromatic aldehydes occurs with relative topicity ul (Scheme 2). The I-hydroxyalkylated 2-pivaloyl-tetrahydroisoquinolines a of u-configuration thus obtained (14 examples) can be converted to free aminoalcohols c of either Ior u-configuration (9 examples; Scheme 3). The depivdloylation with retention (+ u-c) is best achieved by heating in EtOH/KOH, the conversion to 1 -aminoalcohols I-c by treatment with CF,COOH/(CF,CO),O (+ I -pivalates I-b), followed by alkaline saponification or by LiAIH4 reduction of the esters. The configuration of the products is assigned by 'H-NMR spectroscopy, by X-ray crystal structure analysis, by chemical correlation, and by comparison of the chemical properties of the Iand the u-isomers. The diastereoselective hydroxybenzylation of the tetrahydroisoquinoline is used for short syntheses of ushinsunine/ oliveroline (Scheme 4 ) , p-hydrastine, and ophiocarpine/epiophiocarpine (Scheme 6: aporphine, phthalide, and protoberberine alkaloids, respectively).

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Section: U-[i -(2-brom-a-hydroxy-34-dimethoxybenzyl) -I 234-tementioning

confidence: 99%

Section: )unclassified

Section: ( Tert-buiy~)-[i234-terrahydro-67-(dimethoxy) Isochinoliunclassified

Section: 17 U-( Tert-bu~yll-[1234-tetralzydro-l-(a-h~droxy-cc-mrunclassified

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Diasteroselektive Hydroxyalkylierungen in 1‐Stellung von Tetrahydroisochinolinen und Synthese von Aporphin‐, Protoberberin‐ und Phthalid‐Alkaloider

Seebàch¹,

Isabelle²,

Max³

1987

Helvetica Chimica Acta

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Recent Advances in the Photochemistry of the Carbon–Halogen Bond

Lodder

Cornelisse

2009

Patai's Chemistry of Functional Groups

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Trifluoroacetyl‐Containing Scaffolds Assisted in Total Synthesis of Oxostephanine and Thailandine and Their Antimicrobial Activity

Vijitphan,

Makarasen,

Baicharoen

et al. 2024

Asian J Org Chem

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This study is the first to fully synthesize oxostephanine (1) and thailandine (2), two aporphine alkaloids that were originally found in Stephania venosa (Blume) Spreng. The synthesis described in this study utilized commercially available starting materials, namely 2‐bromo‐6‐methoxybenzaldehyde and 3,4‐dihydroxybenzaldehyde. The B‐ring moiety of aporphines was successfully synthesized through the utilization of the Bischler‐Napieralski cyclization process. The synthesis of the C ring in oxoaporphine was accomplished using an order of crucial steps, namely biaryl coupling, incorporation of trifluoroacetyl‐containing scaffolds, and palladium coupling, followed by oxidation using Fremy's salt. The synthesis of oxostephanine (1) and thailandine (2) was successfully achieved in 11 and 12 steps, respectively, resulting in equivalent overall yields of 11.7%. This study aimed to increase amount of interested compounds and explore the biological activity of those compounds. In this study, both compounds were subjected to testing for antibacterial activity using the CLSI standard M100 guideline. Oxostephanine (1) has shown significant antibacterial efficacy against gram‐positive bacteria and bacterial biofilms, as seen by minimum inhibitory concentration (MIC) values ranging from 7.8 to 125 µg/mL. Conversely, higher MIC values of 250 µg/mL indicated that thailandine (2) exhibited limited antimicrobial activity.

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Synthetic photochemistry. Synthesis of (±)oliveroline and (±)ushinsunine

Cited by 16 publications

References 8 publications

Diasteroselektive Hydroxyalkylierungen in 1‐Stellung von Tetrahydroisochinolinen und Synthese von Aporphin‐, Protoberberin‐ und Phthalid‐Alkaloider

Diasteroselektive Hydroxyalkylierungen in 1‐Stellung von Tetrahydroisochinolinen und Synthese von Aporphin‐, Protoberberin‐ und Phthalid‐Alkaloider

Recent Advances in the Photochemistry of the Carbon–Halogen Bond

Trifluoroacetyl‐Containing Scaffolds Assisted in Total Synthesis of Oxostephanine and Thailandine and Their Antimicrobial Activity

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