439-66-7

Basic information

• Product Name: geissoschizine
• Synonyms: geissoschizine;(16E,19E)-16,17,19,20-Tetradehydro-17-hydroxycorynan-16-carboxylic acid methyl ester
• CAS NO: 439-66-7
• Molecular Formula: C₂₁H₂₄N₂O₃
• Molecular Weight: 352.42686
• Mol File: 439-66-7.mol
• Article Data: 13

Chemical Properties

• Boiling Point: 528.3°Cat760mmHg
• Flash Point: 273.3°C
• Appearance: /
• Density: 1.26g/cm³
• Vapor Pressure: 3E-11mmHg at 25°C
• Refractive Index: 1.634
• CAS DataBase Reference: geissoschizine(CAS DataBase Reference)
• NIST Chemistry Reference: geissoschizine(439-66-7)
• EPA Substance Registry System: geissoschizine(439-66-7)

Safety Data

• Hazardous Substances Data: 439-66-7(Hazardous Substances Data)

Usage

InChI:InChI=1/C21H24N2O3/c1-3-13-11-23-9-8-15-14-6-4-5-7-18(14)22-20(15)19(23)10-16(13)17(12-24)21(25)26-2/h3-7,12,16-17,19,22H,8-11H2,1-2H3/b13-3-/t16-,17?,19-/m0/s1

Upstream product

• 236750-89-3 tert-butyl [3S^*-(3α,5β,15α,20β)]-3,4,5,6,14,15,20-heptahydro-20-(1'S-1'-ethan-1'-ol)-15-(methyl acetate)-21-oxo-indolo[2,3-a]quinolizine-5-carboxylate 
• 236750-88-2 tert-butyl [3S^*-(3α,5β,15α,20β)]-3,4,5,6,14,15,20-heptahydro-20-(ethan-1-one)-15-(methyl acetate)-21-oxo-indolo[2,3-a]quinolizine-5-carboxylate 
• 236750-90-6 tert-butyl 20E-[3S^*-(3α,5β,15α)]-3,4,5,6,14,15-hexahydro-15-(methyl acetate)-20-ethylidene-21-oxo-indolo[2,3-a]quinolizine-5-carboxylate 
• 236750-91-7 tert-butyl 20E-[3S^*-(3α,5β,15α)]-3,4,5,6,14,15,21-heptahydro-15-(methyl acetate)-20-ethylidene-indolo[2,3-a]quinolizine-5-carboxylate 
• 236750-87-1 tert-butyl [3S^*-(3α,5β)]-3,4,5,6-tetrahydro-3-(methyl but-2'-enoate-4'-yl)-1H-pyrido[3,4-b]indole-5-carboxylate 
• 236750-86-0 [3S^*-(3α,5β)]-3,4,5,6-tetrahydro-3-(methyl but-2'-enoate-4'-yl)-1H-pyrido[3,4-b]indole-5-carboxylic acid 
• 236750-92-8 20E-[3S^*-(3α,5β,15α)]-3,4,5,6,14,15,21-heptahydro-15-(methyl acetate)-20-ethylidene-indolo[2,3-a]quinolizine-5-carboxylic acid 
• 153-94-6 D-tryptophan 
• 79233-46-8 [(2S,3R,12bS)-3-((R)-1-Methoxy-ethyl)-4-oxo-1,2,3,4,6,7,12,12b-octahydro-indolo[2,3-a]quinolizin-2-yl]-acetonitrile 
• 79233-46-8 [(2S,3S,12bS)-3-((R)-1-Methoxy-ethyl)-4-oxo-1,2,3,4,6,7,12,12b-octahydro-indolo[2,3-a]quinolizin-2-yl]-acetonitrile 
• 79228-03-8 (2R,3R,12bS)-2-Hydroxymethyl-3-((R)-1-methoxy-ethyl)-2,3,6,7,12,12b-hexahydro-1H-indolo[2,3-a]quinolizin-4-one 
• 79228-03-8 (2R,3S,12bS)-2-Hydroxymethyl-3-((R)-1-methoxy-ethyl)-2,3,6,7,12,12b-hexahydro-1H-indolo[2,3-a]quinolizin-4-one 
• 79227-99-9 2-[2-((2R,3R)-2-Bromo-3-methoxy-butyryl)-2,3,4,9-tetrahydro-1H-β-carbolin-1-ylmethyl]-malonic acid diethyl ester 
• 79228-01-6 (3R,12bR)-3-((S)-1-Methoxy-ethyl)-4-oxo-3,4,6,7,12,12b-hexahydro-1H-indolo[2,3-a]quinolizine-2,2-dicarboxylic acid diethyl ester 

Downstream Products

• 483-04-5 ajmalicine 
• 25532-45-0 19-Epiajmalicine 
• 6474-90-4 tetrahydroalstonine 
• 6519-27-3 16R-E-isositsirikine 
• 60031-91-6 16-epi E isositsirikine 
• 6393-66-4 (+)-16-epi-pleiocarpamine 

Relevant articles and documents

Studies on plants containing indole alkaloids. VI. Minor bases of Uncaria rhynchophylla Miq

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Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for the Total Synthesis of (?)-17-nor-Excelsinidine

We report the first total synthesis of (?)-17-nor-excelsinidine, a zwitterionic monoterpene indole alkaloid that displays an unusual N4?C16 connection. Inspired by the postulated biosynthesis, we explored an oxidative coupling approach from the geissoschizine framework to forge the key ammonium–acetate connection. Two strategies allowed us to achieve this goal, namely an intramolecular nucleophilic substitution on a 16-chlorolactam with the N4 nitrogen atom or a direct I2-mediated N4?C16 oxidative coupling from the enolate of geissoschizine.

Palladium catalyzed reductive Heck coupling and its application in total synthesis of (?)-17-nor-excelsinidine

Monoterpene indole alkaloids, bearing a highly substituted piperidine ring, are a structurally diverse class of bioactive natural products, found in various parts of the world. Herein, we reported the construction of the key piperidine ringviapalladium catalyzed reductive Heck coupling with a goodsynselective manner, avoiding the usage of stoichiometric, highly toxic, air sensitive and moisture sensitive Ni(COD)2. To further showcase the value of this methodology, we realized the total synthesis of the structurally unique zwitterionic monoterpene indole alkaloid (?)-17-nor-excelsinidine in 9 steps, in which the key ammonium-acetate connection (N4-C16) of (?)-17-nor-excelsinidine was constructedviaoxidative coupling in excellent yield and high regioselectivity under NBS/pyridine from the enolate of geissoschizine.

Bioinspired Divergent Oxidative Cyclizations of Geissoschizine: Total Synthesis of (–)-17-nor-Excelsinidine, (+)-16-epi-Pleiocarpamine, (+)-16-Hydroxymethyl-Pleiocarpamine and (+)-Taberdivarine H

We report a full account of our efforts towards bioinspired oxidative cyclizations of geissochizine and analogs to mimic the biosynthesis of the mavacuran, akuammilan, and excelsinidine groups of monoterpene indole alkaloids. The construction of the A,B,C,D ring system of geissoschizine was first achieved by merging two known syntheses of this alkaloid. Modified Ma's oxidative conditions (KHMDS/I2) applied directly to geissoschizine induced formation of the N4–C16 bond encountered in the excelsinidines core. Identical conditions applied to C16-dimethylmalonate-containing N4-quaternized substrates ended in the formation of the mavacurans core (N1–C16 bond). With this unified oxidative cyclization strategy: (–)-17-nor-excelsinidine, (+)-16-epi-pleiocarpamine, (+)-16-hydroxymethyl-pleiocarpamine, 16-formyl-pleiocarpamine and (+)-taberdivarine H were synthetized. We also report a shortened total synthesis of 16-epi-pleiocarpamine compared to our preliminary communication from a C16-monoester analog. Alternatively, 17-nor-excelsinidine was synthesized via an intramolecular nucleophilic substitution of a 7-membered ring α-chlorolactam prepared from 16-desformyl-geissoschizine.