501-02-0

Basic information

• Product Name: (2R,6R)-2-methyl-6-prop-1-enyl-piperidine
• Synonyms: (2R,6R)-2-methyl-6-prop-1-enyl-piperidine;(-)-Pinidine;(2R)-2-Methyl-6α-[(E)-1-propenyl]piperidine;2α-Methyl-6α-[(E)-1-propenyl]piperidine;Pinidine
• CAS NO: 501-02-0
• Molecular Formula: C9H17N
• Molecular Weight: 0
• Mol File: 501-02-0.mol
• Article Data: 11

Chemical Properties

• Boiling Point: 183.2°Cat760mmHg
• Flash Point: 56.1°C
• Appearance: /
• Density: 0.879g/cm³
• Vapor Pressure: 0.779mmHg at 25°C
• Refractive Index: 1.503
• CAS DataBase Reference: (2R,6R)-2-methyl-6-prop-1-enyl-piperidine(CAS DataBase Reference)
• NIST Chemistry Reference: (2R,6R)-2-methyl-6-prop-1-enyl-piperidine(501-02-0)
• EPA Substance Registry System: (2R,6R)-2-methyl-6-prop-1-enyl-piperidine(501-02-0)

Safety Data

• Hazardous Substances Data: 501-02-0(Hazardous Substances Data)

Usage

Description

A piperidine alkaloid isolated from Pinus jeffreyi, P. sabiniana Doug!., and P. torreyana, this base is a colourless liquid which is laevorotatory with [Ql~~9 - 10.5° and [Ql~j5 - 23.4° (c 1.88, EtOH). It yields a crystalline hydrochloride as colourless needles from EtOH-AcOEt, m.p. 244-6°C and a methiodide, m.p. 214-8°C. The structure has been determined by spectroscopic methods as 2-methyl-6-( trans-2-propeny I)-piperidine.

References

Tallent, Stromberg, Horning.,J. Arner. Chern. Soc., 77,6361 (1955) Tallent, Horning., ibid, 78,4467 (1956) Hill, Chan, Joule., Tetrahedron, 21,147 (1965)

InChI:InChI=1/C9H17N/c1-3-5-9-7-4-6-8(2)10-9/h3,5,8-10H,4,6-7H2,1-2H3/b5-3+/t8-,9+/m1/s1

Upstream product

• 96838-85-6 1-Methyl-octa-5,6-dienylamine 
• 96838-84-5 Nona-6,7-dien-2-one oxime 
• 96838-83-4 Nona-6,7-dien-2-one 
• 20077-29-6 (2S,6S)-6-Methyl-piperidine-2-carboxylic acid ethyl ester 
• 55048-74-3 (4E)-hepta-4,6-dien-1-ol 
• 74930-35-1 hepta-4(E),6-dienecarbonitrile 
• 445398-83-4 nona-6(E),8-dien-2-amine 
• 118014-72-5 (6R,7S,8S)-7,8-Bis<(methoxymethyl)oxy>-6-(1,3-dioxo-2-azaindan-2-yl)-1-nonene 
• 118014-73-6 <2R,6R,2(1S,2S)>-2-<1,2-Bis<(methoxymethyl)oxy>propyl>-6-methyl-N-(p-tolylsulfonyl)piperidine 
• 118014-75-8 <2R,6R,2(4S,5S)>-2-(4-Methyl-2-thioxo-1,3-dioxolanyl)-6-methyl-N-(p-tolylsulfonyl)piperidine 
• 118014-74-7 <2R,6R,2(1S,2S)>-2-<1,2-Dihydroxypropyl>-6-methyl-N-(p-tolylsulfonyl)piperidine 
• 118014-71-4 (2S,3S,4S)-2,3-Bis<(methoxymethyl)oxy>-8-nonen-4-ol 
• 117941-19-2 (2S,3S)-2,3-Bis-methoxymethoxy-non-8-en-4-ol 
• 117941-30-7 <2R,6R,2(1S,2S)>-2-<1,2-Bis<(methoxymethyl)oxy>propyl>-6-methylpiperidine 

Relevant articles and documents

Intramolecular Hydroamination/Cyclization of Conjugated Aminodienes Catalyzed by Organolanthanide Complexes. Scope, Diastereo- and Enantioselectivity, and Reaction Mechanism

Organolanthanide complexes of the general type Cp′ 2LnCH(TMS)2 (Cp′ = η5-Me 5C5; Ln = La, Sm, Y; TMS = SiMe3) and CGCSmN(TMS)2 (CGC = Me2Si(η5-Me 4C5)(tBuN)) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization of primary and secondary amines tethered to conjugated dienes. The rates of aminodiene cyclizations are significantly more rapid than those of the corresponding aminoalkenes. This dienyl group rate enhancement as well as substituent group (R) effects on turnover frequencies is consistent with proposed transition state electronic demands. Kinetic and mechanistic data parallel monosubstituted aminoalkene hydroamination/cyclization, with turnover-limiting C=C insertion into the Ln-N bond to presumably form an Ln-η3 allyl intermediate, followed by rapid protonolysis of the resulting Ln-C linkage. The rate law is first-order in [catalyst] and zero-order in [aminodiene]. However, depending on the particular substrate and catalyst combination, deviations from zero-order kinetic behavior reflect competitive product inhibition or self-inhibition by substrate. Lanthanide ionic radius effects and ancillary ligation effects on turnover frequencies suggest a sterically more demanding Ln-N insertion step than in aminoalkene cyclohydroamination, while a substantially more negative ΔS? implies a more highly organized transition state. Good to excellent diastereoselectivity is obtained in the synthesis of 2,5-trans-disubstituted pyrrolidines (80% de) and 2,6-cis-disubstituted piperidines (99% de). Formation of 2-(prop-1-enyl)piperidine using the chiral C1-symmetric precatalyst (S)-Me2Si(OHF)(CpR* )SmN(TMS)2 (OHF = η5-octahydrofluorenyl; Cp = η5-C5H3; R* = (-)-menthyl) proceeds with up to 71% ee. The highly stereoselective feature of aminodiene cyclization is demonstrated by concise syntheses of naturally occurring alkaloids, (±)-pinidine and (+)-coniine from simple diene precursors.

The use of the aza-Diels-Alder reaction in the synthesis of pinidine and other piperidine alkaloids

The imine Ph2CHN=CHCO2Et, generated from benzhydrylamine and ethyl glyoxylate, provides a Diels-Alder adduct with 1,3-pentadiene from which a range of cis-2,6-disubstituted piperidines can be accessed; the benzhydryl group confers high diastereocontrol for derivatising the six-membered ring, allowing access to 2,5,6-trisubstituted piperidines, and to 2,6-disubstituted piperidines such as pinidine.

Stereocontrolled syntheses of piperidine derivatives using diastereoselective reactions of chiral 1,3-oxazolidines with grignard reagents: Asymmetric syntheses of the pinidine enantiomers

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