139341-79-0

Upstream product

• 85-63-2 (R)-laudanosine 
• 124293-99-8 4H-6-carbethoxy-1,2,9,10-tetramethoxy-5,6,6a,7-tetrahydrodibenzo[de,g]quinoline 
• 1699-51-0 laudanosine 
• 5630-11-5 (+/-)-glaucine 
• 16620-96-5 2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 
• 38973-42-1 6,7-dimethoxy-2-methylisoquinoline-1,3(2H,4H)-dione 
• 3809-00-5 4,5-dimethoxyhomophthalic acid 
• 134619-96-8 C₁₂H₁₇BF₃NO₂ 
• 35690-87-0 1,2,3,8,9,9a-hexahydro-5,6-dimethoxy-1-methyl-7H-benzoquinolin-7-one 
• 80941-67-9 7-Formyldehydroglaucine 
• 80955-23-3 7-Hydroxymethyldehydroglaucine 
• 22212-26-6 dehydroglaucine 
• 132974-52-8 1,2,9,10-tetramethoxy-5-oxonoraporphine 
• 7664-93-9 sulfuric acid 

Downstream Products

• 475-81-0 glaucine 
• 475-81-0 (-)-(R)-glaucine 
• 22212-26-6 dehydroglaucine 
• 5574-24-3 oxoglaucine 
• 34647-65-9 pontevedrine 
• 103769-59-1 corrunine 
• 28230-74-2 2,9-dimethoxy-6-methyl-5,6,6a,7-tetrahydro-4H-dibenzo[de,g]quinoline-1,10-diol 
• 2755-00-2 thaliporphine 
• 82644-87-9 7-(p-Methoxy-phenoxy)-dehydroglaucin 
• 82644-89-1 7-(2,5-Dihydroxy-phenyl)-dehydroglaucin 
• 82644-88-0 7-(p-Hydroxy-phenoxy)-dehydroglaucin 

Relevant academic research and scientific papers

Stereoselective synthesis of aporphine alkaloids using a hypervalent iodine(III) reagent-promoted oxidative nonphenolic biaryl coupling reaction. Total synthesis of (S)-(+)-glaucine

The aporphine alkaloid (+)-glaucine (8a) and two other analogues 8b,c have been synthesized in good yield and high ee from the appropriate 1,2-diarylethylamine derivatives, which were in turn prepared using (S)-(+)-phenylglycinol as chiral support. Next, a sequence of simple transformations: N-alkylation with bromoacetaldehyde diethyl acetal, N-methylation, Pommeranz-Fritsch cyclization, and ionic hydrogenation led to the key intermediate, optically active, 1-benzyltetrahydroisoquinolines 7a-c. The final C-ring closure step was performed by C-C biaryl bond formation by an hypervalent iodine(III) reagent promoted oxidative coupling, affording the target heterocycles 8a-c in good yields and with no racemization at the formerly created stereogenic center.

Tributyltinhydride-induced intramolecular radical cyclization to aporphines and 5-oxoaporphines

A new synthesis of aporphines by tributyltinhydride-induced intramolecular radical cyclization of bromobenzylisoquinolines is described. This route to aporphines also allowed the first total synthesis of a 5-oxoaporphine.

A new synthesis of the aporphine alkaloids (±)-glaucine and (±)-nantenine

(±)-Glaucine and (±)-nantenine were newly synthesized by aromatization of cyclohexenone derivatives which were prepared by [3C+3C] condensation of two units, 1,1-bis(ethylthio)-2-propanone and the Mannich base.

A new synthesis of the aporphine alkaloids (±)-glaucine and (±)-nantenine. Application of [3C + 3C] annelation to the D-ring formation

A [3C + 3C] annelation using 1,1-bis(ethylthio)-2-propanone was applied to a new synthesis of the aporphine alkaloids. Condensation of the ketone with the Mannich base gave two isomeric cyclohexenones, which were converted into the aporphine framework by aromatization. (±)-Glaucine and (±)-nantenine were prepared by employing this new aromatic synthesis.

In vitro functional evaluation of isolaureline, dicentrine and glaucine enantiomers at 5-HT2 and α1 receptors

Compounds with activity at serotonin (5-hydroxytryptamine) 5-HT2 and α1 adrenergic receptors have potential for the treatment of central nervous system disorders, drug addiction or overdose. Isolaureline, dicentrine and glaucine enantiomers were synthesized, and their in vitro functional activities at human 5-HT2 and adrenergic α1 receptor subtypes were evaluated. The enantiomers of isolaureline and dicentrine acted as antagonists at 5-HT2 and α1 receptors with (R)-isolaureline showing the greatest potency (pKb?=?8.14 at the 5-HT2C receptor). Both (R)- and (S)-glaucine also antagonized α1 receptors, but they behaved very differently to the other compounds at 5-HT2 receptors: (S)-glaucine acted as a partial agonist at all three 5-HT2 receptor subtypes, whereas (R)-glaucine appeared to act as a positive allosteric modulator at the 5-HT2A receptor.

Total Synthesis of Tetrahydroisoquinoline-Based Bioactive Natural Products Laudanosine, Romneine, Glaucine, Dicentrine, and Their Unnatural Analogues Isolaudanosine and Isoromneine

Starting from suitably substituted homophthalic acids, total synthesis of titled alkaloids have been demonstrated in very good yields. The obtained natural products laudanosine and romneine were utilized to accomplish synthesis of two isoquinoline-based alkaloids glaucine and dicentrine. Base-induced selective generation of two different types of benzylic carbanions, their coupling reactions with 3,4-dimethoxybenzyl mesylate, and the regioselective iodination followed by intramolecular aryl-aryl coupling reactions to form the fused biaryl systems were the strategic steps.

Application of the hypervalent iodine reagent to the synthesis of some pentasubstituted aporphine alkaloids

The oxidative biaryl coupling of various N-substituted 1- benzyltetrahydroisoquinolines to the corresponding aporphines by the hypervalent iodine reagent was studied. The study sheds light on the unifying mechanism of the reaction illustrating the requirement of the p-p coupling via the six-membered transition state as the initial step. The finding was applied to the synthesis of some pentasubstituted aporphine alkaloids. Georg Thieme Verlag Stuttgart.

The efficient synthesis of morphinandienone alkaloids by using a combination of hypervalent iodine(III) reagent and heteropoly acid

The non-phenolic coupling reaction of benzyltetrahydroisoquinolines (laudanosine derivatives) by using a hypervalent iodine(III) reagent is described. In general, chemical oxidation of laudanosine gives glaucine. In contrast to general chemical oxidizing reagent systems, the novel use of reagent combination of phenyliodine bis(trifluoroacetate) (PIFA), and heteropoly acid (HPA) afforded morphinandienone alkaloids in excellent yields. In order to achieve the coupling reaction with simple reaction procedure, the use of HPA supported on silica gel instead of HPA was demonstrated and sufficient yield was exerted again. The present reagent system, PIFA/HPA, was also applied to the oxidation of other non-phenolic benzyltetrahydroisoquinolines and the high yield conversion to morphinandienones was accomplished.

Synthesis of (±)-Glaucine and (±)-Neospirodienone via an One-Pot Bischler-Napieralski Reaction and Oxidative Coupling by a Hypervalent Iodine Reagent

Condensation of 3,4-dimethoxybenzeneethanamine (3d) and various benzeneacetic acids, i.e., 4a-e, via a practical and efficient one-pot Bischler-Napieralski reaction, followed by NaBH4 reduction, produced a series of 1-benzyl-1,2,3,4-tetrahydroisoquinolines, i.e., 5a-e, in satisfactory yields (Scheme 3). Oxidative coupling of the N-acyl and N-methyl derivatives 6a-e of the latter with hypervalent iodine ([IPh(CF 3COO)2]) yielded products with two different skeletons (Scheme 4). The major products from N-acyl derivatives 6a-c were (±)-N-acylneospirodienones 2a-c, while the minor was the 3,4-dihydroisoquinoline 7. (±)-Glaucine (1), however, was the major product starting from N-methyl derivative 6e. Possible reaction mechanisms for the formation of these two types of skeleton are proposed (Scheme 5).

Enantioselective synthesis of (R)-(-)-laudanosine and (R)-(-)-glaucine from L-ascorbic acid

L-Ascorbic acid 1 was converted into L-gulonolactone 2 by catalytic hydrogenation. Treatment of 2 with 3,4-dimethoxyphenylethyl amine 3 afforded amide 4, which in several steps was transformed into the title alkaloids in good enantiomeric excesses. Also, chromium(III) oxide is proposed as an effective catalyst for the conversion of (R)-(-)-laudanosine into (R)-(-)-glaucine.