Simplified analogs of lysergic acid. V. Derivatives of N,N-diethyl-1-methyl-9H-indeno-1,2,3,9a-tetrahydro[2,1-b]pyridine-3-carboxamide

Craig, J. C.; Dinner, A.; Mulligan, P. J.

doi:10.1021/jo00925a016

J. Org. Chem.

1974

DOI: 10.1021/jo00925a016

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Simplified analogs of lysergic acid. V. Derivatives of N,N-diethyl-1-methyl-9H-indeno-1,2,3,9a-tetrahydro[2,1-b]pyridine-3-carboxamide

J. C. Craig¹,

A. Dinner²,

P. J. Mulligan³

Abstract: The synthesis of the simplified analog of lysergic acid diethylamide, !V,lV-diethyl-l-methyl-9.f/-indeno-l,2,3-9a-tetrahydro[2,l-6]pyridine-3-carboxamide (6b), in which the ß-arylethylamine moiety exists twice with reference to one benzene nucleus, is described. The starting material (indene) was converted to the tricyclic intermediate ethyl 4a-hydroxy-4-keto-l-methyl-9.fi-indeno-1,2,3,4,4a,9a-hexahydro[2,l-6]pyridine-3-carboxylate (28a) via a six-step sequence and thence to the title compound 6b in four steps… Show more

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Cited by 13 publications

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“…C NMR (125 MHz, CDCl 3 ) δ 27.6, 38.5, 123.4, 123.6, 125.7, 126.6, 140.7, 143.1, 143.4, 144.7, 196.1; IR (neat) 3069, 2922,1673, 1380, 1247, 766 cm -1 . 1 H NMR and 13 C NMR spectra are in agreement with those described in the literature 14. …”

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confidence: 89%

Siloxyalkyne-Alkene Metathesis: Rapid Access to Highly Functionalized Enones

2001

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The advent of structurally defined metal alkylidenes capable of promoting p-bond metathesis under mild conditions, with high efficiency and functional group compatibility, has had a profound effect on modern organic synthesis.[1] Among a range of synthetically useful transformations, the enyne metathesis is particularly noteworthy for the ability to assemble two carbon ± carbon bonds in a single step starting from appropriate alkyne and alkene components. [2] However, elaboration of the full synthetic potential of this process has been limited largely to the use of simple, unactivated enyne precursors. [3] We report here a mechanistically intriguing example of the participation of siloxyalkynes in the intramolecular Ru-catalyzed metathesis with terminal alkenes, which resulted in the development of a new method for the synthesis of highly functionalized enones III starting from readily accessible acyclic precursors I (Scheme 1). [4] Furthermore, this approach represents a novel method for the construction of silyldienol ethers II starting directly from enyne I, conceptually different from the conventional enol silylation of carbonyl compounds. Scheme 1. Projected outcome of the siloxyalkyne ± alkene metathesis.Our studies began with the preparation of a model cyclization substrate 2 (Scheme 2). Construction of siloxyalkyne 2 was accomplished according to a modified Kowalski protocol [5] entailing the initial conversion of ester 1 to the corresponding dibromoketone, followed by generation of the ynolate anion (LHMDS, nBuLi) and silylation with TIPSOTf to afford enyne 2.Scheme 2. Preparation of siloxyalkyne 2. LiHMDS lithium bis(trimethylsilyl)amide, TIPSOTf triisopropyl trifluoromethanesulfonate. We next systematically examined several olefin metathesis catalysts in order to achieve the desired conversion of siloxyalkyne 2 to the corresponding diene 3 [Eq. (1)]. Following the unsuccessful attempts to employ either the original Grubbs or the Schrock Mo-catalyst 6 [7] (Table 1, entries 1 and 2), we turned our attention to the recently developed Ru-complexes bearing highly nucleophilic imidazolylidene ligands. [8] To our delight, both 7 [9] and 8 [10] were found to promote the desired transformation, nevertheless they displayed a noticeable difference in reactivity. [11] The reaction proceeded to completion in the presence of 8 (5 mol %) over a period of 13 h at 20 8C, and within minutes at 60 8C (entries 4, 5). The cyclization employing complex 7 was [6] a) L.

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confidence: 89%

Siloxyalkyne-Alkene Metathesis: Rapid Access to Highly Functionalized Enones

2001

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Indium(III)‐Catalyzed Cyclization of Aromatic 5‐Enynamides: Facile Synthesis of 2‐Aminonaphthalenes, 2‐Amino‐1H‐indenes, and 2,3‐Dihydro‐1H‐indeno[2,1‐b]pyridines

et al. 2015

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Indium(III)‐catalyzed cyclization reactions of aromatic 5‐enynamides were studied. Indium triflate enabled the efficient synthesis of 2‐aminonaphthalenes and 2‐amino‐1H‐indenes from aromatic N‐methyl‐N‐tosyl‐ynamides bearing an ortho‐vinyl and ‐isobutenyl group, respectively. The aromatic N‐3‐arylpropargylynamides bearing an ortho‐gem‐dihalovinyl subunit underwent a tandem cyclization/carbobromination reaction in the presence of indium tribromide to provide the dibrominated 2,3‐dihydro‐1H‐indeno[2,1‐b]pyridine derivatives in good yields.

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ChemInform Abstract: SIMPLIFIED ANALOGS OF LYSERGIC ACID PART 5, DERIVATIVES OF N,N‐DIETHYL‐METHYL‐9H‐INDENO‐1,2,3,9A‐TETRAHYDRO(2,1‐B)PYRIDINE‐3‐CARBOXAMIDE

Craig¹,

Dinner²,

Mulligan³

1974

Chemischer Informationsdienst

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Simplified analogs of lysergic acid. V. Derivatives of N,N-diethyl-1-methyl-9H-indeno-1,2,3,9a-tetrahydro[2,1-b]pyridine-3-carboxamide

Cited by 13 publications

References 10 publications

Siloxyalkyne-Alkene Metathesis: Rapid Access to Highly Functionalized Enones

Siloxyalkyne-Alkene Metathesis: Rapid Access to Highly Functionalized Enones

Indium(III)‐Catalyzed Cyclization of Aromatic 5‐Enynamides: Facile Synthesis of 2‐Aminonaphthalenes, 2‐Amino‐1H‐indenes, and 2,3‐Dihydro‐1H‐indeno[2,1‐b]pyridines

ChemInform Abstract: SIMPLIFIED ANALOGS OF LYSERGIC ACID PART 5, DERIVATIVES OF N,N‐DIETHYL‐METHYL‐9H‐INDENO‐1,2,3,9A‐TETRAHYDRO(2,1‐B)PYRIDINE‐3‐CARBOXAMIDE

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