517-81-7

Basic information

• Product Name: uleine
• Synonyms: uleine;(12S)-2-Methyl-6-methylene-12-ethyl-1β,5β-methano-2,3,4,5,6,7-hexahydro-1H-azocino[4,3-b]indole;[12S,(+)]-12-Ethyl-2,3,4,5,6,7-hexahydro-2-methyl-6-methylene-1β,5β-methano-1H-azocino[4,3-b]indole
• CAS NO: 517-81-7
• Molecular Formula: C18H22N2
• Molecular Weight: 266.3807
• Mol File: 517-81-7.mol
• Article Data: 11

Chemical Properties

• Boiling Point: 437.6°Cat760mmHg
• Flash Point: 218.5°C
• Appearance: /
• Density: 1.14g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.639
• CAS DataBase Reference: uleine(CAS DataBase Reference)
• NIST Chemistry Reference: uleine(517-81-7)
• EPA Substance Registry System: uleine(517-81-7)

Safety Data

• Hazardous Substances Data: 517-81-7(Hazardous Substances Data)

Usage

Description

An Aspidosperma alkaloid, this base occurs in several members of this species and particularly in A. ulei. It forms colourless crystals having the double melting point given above. It is slightly dextrorotatory with [α]25D + 11.5° (CHCI3 ) and gives an ultraviolet spectrum having a broad absorption maximum at 307-8 Mu.1 and a second maximum at 316 IT1J.1. The hydrochloride is crystalline with m.p. 241-2°C and the tnethiodide has m.p. 204-6°C. Oxidation with KMn04 yields formaldehyde indicative of an exocyc1ic methylene group.

References

Schmutz, Hunziker, Hirt., Helv. Chim. Acta, 40, 1189 (1957) Schmutz, Hunziker, Hirt., ibid, 41, 288 (1958) Buchi, Warnhoff.,J. Amer. Chem. Soc., 81,4433 (1959) Ondetti, Deulofeu., Tetrahedron Lett., No.7, 1 (1959) Synthesis: Wilson et ai., Chem. Commun., 584 (1968)

InChI:InChI=1/C18H22N2/c1-4-12-13-9-10-20(3)18(12)16-14-7-5-6-8-15(14)19-17(16)11(13)2/h5-8,12-13,18-19H,2,4,9-10H2,1,3H3/t12-,13-,18+/m0/s1

Upstream product

• 78175-17-4 1-[3-Ethyl-2-(1H-indol-3-yl)-1-methyl-piperidin-4-yl]-ethanone 
• 5515-77-5 4-ethyl-2-cyclohexen-1-one 
• 5441-51-0 4-ethylcyclohexanone 
• 50-00-0 formaldehyd 
• 74627-60-4 (2S,3S)-2-(1H-Indol-3-yl)-3-(2-methanesulfonyloxy-ethyl)-4-(2-methyl-[1,3]dioxolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid benzyl ester 
• 74629-74-6 (2S,3S)-3-Ethoxycarbonylmethyl-2-(1H-indol-3-yl)-4-(2-methyl-[1,3]dioxolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid benzyl ester 
• 74627-61-5 (2R,3R)-3-(2-Hydroxy-ethyl)-2-(1H-indol-3-yl)-4-(2-methyl-[1,3]dioxolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid benzyl ester 
• 73795-54-7 3r-hydroxy-6t-indol-3-yl-4-(2-methyl-[1,3]dioxolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid benzyl ester 

Downstream Products

• 86533-27-9 Ulein-N^b-oxid 
• 19046-20-9 1,13-Dihydro-ulein 

Relevant articles and documents

Two-Carbon Ring Expansion of Cyclobutanols to Cyclohexenones Enabled by Indole Radical Cation Intermediate: Development and Application to a Total Synthesis of Uleine

A single-electron transfer (SET) oxidation of indole or benzo[b]thiophene to a radical cation reverses the intrinsic polarity of these π-excessive bicyclic heteroarenes. Here we report an oxidative two-carbon homologation of cyclobutanols to cyclohexenones under a visible-light photoredox catalysis. 1-(Indol-2-yl)cyclobutan-1-ols are converted to 2,3,4,9-tetrahydro-1H-carbazol-1-ones, important structural motifs found in alkaloids and pharmaceuticals, with a broad substrate scope. A mechanistic study suggests that the reaction is initiated by an SET from an indole to an excited acridinium salt to generate the radical cation, which is followed by two consecutive 1,2-alkyl migrations and a rearomatization. Benzo[b]thiophene-substituted cyclobutanols are similarly converted to 2,3-dihydrodibenzo[b,d]thiophen-4(1H)-ones. A total synthesis of (±)-uleine featuring this ring-expansion process is documented.

Palladium-Catalyzed Ullmann Cross-Coupling/Tandem Reductive Cyclization Route to Key Members of the Uleine Alkaloid Family

The trisubstituted cyclohexenone 12, generated through a palladium-catalyzed Ullmann cross-coupling reaction between o-iodonitrobenzene and a 4,5-trans-disubstituted 2-iodo-2-cyclohexen-1-one, engaged in a tandem reductive cyclization process upon exposur

A New Cationic Domino Process to (±)-Uleine

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