Dien‐Synthesen arylierter Diene. Die Dimerisation von β‐Phenyl‐butadien

Alder, Kurt; Haydn, Joseph

doi:10.1002/jlac.19505700119

Cited by 32 publications

(8 citation statements)

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“…The thermal addition of diene 16 to methacrolein gave a pair of isomers in a 9:1 ratio (NMR).7 Reaction of this mixture with SnCl4 in benzene caused rearrangement only of the major 16 17 18…”

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confidence: 99%

“…at 1.05), 2.65, 2.83 (broad doublet, 2 H, allylic methine), 9.16 and 9.33 (singlets, 1 H. total, CHO, ca. 1:9 ratio of 18/17):" MS m/e (rel intensity) 232 (M+, 15), 203 (M -CHO, 42), 189 (16). 175 (10), 162 (74), 147 (21), 133 (28), 119 (28), 105 (46), 94 (61), 91 (84).…”

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confidence: 99%

“…Drying and concentration gave a golden yellow liquid which was distilled to separate 8.770 g (58%) of ketone 2 as a water-white liquid: bp 54.5-55 °C (5.2 mm); IR (neat) 1740 (C=0), 2970, 2880,1460,1380,967 cm"1; NMR (90 MHz, CC14) 0.97 (d, J = 7 Hz, 3 H, CH3CHC=0), 1.10 (s, 3 H, CH3), 1.19 (s, 3 H, CH3), 1.2-2.0 (m, 7 H, aliphatic CH, including a partially overlapped quartet at 1.83, J = 7 Hz, due to CHC=0); MS m/e (rel intensity) 152 (M+, 17), 137 (M -CH3, 3), 123 (1), 109 (14), 95 (100), 94 (34), 82 (18), 81 (23). 69 (21), 67 (26), 55 (16). 53 Attempted Epimerization of 2 and Formation of 2-d A solution of NaOMe, prepared from 23 mg (1.0 mmol) of Na, and 761 mg (5.0 mmol) of 2 in 25 mL of MeOH, was stirred at room temperature under N2.…”

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Rearrangements in Lewis acid catalyzed Diels-Alder reactions. Route to substituted bicyclo[2.2.1]heptanones

Baldwin¹,

Lusch²

1979

J. Org. Chem.

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Rearrangements in Lewis acid catalyzed Diels-Alder reactions. Route to substituted bicyclo[2.2.1]heptanones

Baldwin¹,

Lusch²

1979

J. Org. Chem.

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“…One of the first and simplest procedures for the synthesis of 7 in high yields was reported by Alder and Haydn using a potassium bisulfate-mediated dehydration of 2,3-diphe-nylbutane-2,3-diol (1). 2 Dodson et al 3 and Baldwin and Lusch, 4 however, were unable to reproduce these results.…”

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A Novel and Facile Synthesis of 2,3-Diphenylbuta-1,3-diene

Wagner¹,

Brinker²

2001

Synthesis

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An inexpensive, simple, and high yield synthesis of the title compound is reported. In addition, some mechanistic insights into the dehydration and accompanying reactions of 2,3-diphenylbutane-2,3-diol are presented.2,3-Diphenylbuta-1,3-diene (7) is a compound of considerable interest to both industrially and academically oriented organic chemists. 1 Unfortunately, most of the numerous published syntheses of 7 are time-and moneyconsuming multistep reactions that give low yields or use expensive chemicals.One of the first and simplest procedures for the synthesis of 7 in high yields was reported by Alder and Haydn using a potassium bisulfate-mediated dehydration of 2,3-diphenylbutane-2,3-diol (1). 2 Dodson et al. 3 and Baldwin and Lusch, 4 however, were unable to reproduce these results.In a general dehydration procedure (Scheme 1) using acidic conditions, 5 the elimination reaction proceeds likely via carbocation 2, which is deprotonated to 4. In a second step, 4 is dehydrated to give diene 7, but not exclusively. This was shown by a detailed product analysis. In addition, 3,3-diphenylbutan-2-one (6) and 3-methyl-2-phenylindene (8) are usually found as byproducts.The formation of 6 can best be explained by a simple Wagner-Meerwein-rearrangement (WMR; a pinacol rearrangement) of carbocation 2 to carbocation 3 and a subsequent deprotonation to yield ketone 6. 6 The substituted indene 8 is thought to derive from 1 via the delocalized cationic intermediates 5 by an intramolecular FriedelCrafts alkylation (FCA) reaction. 7 Cation 5 might also be Scheme 1Downloaded by: University of Pittsburgh. Copyrighted material.

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“…Nonetheless, synthesis of ortho ‐terphenyls remains challenging due to steric hindrance of two ortho ‐standing aromatic rings. Existing synthetic routes towards ortho ‐terphenyls include Diels‐Alder reactions followed by aromatization or Ullman‐coupling . More recent reports use Hiyama, Kumada, Suzuki, and Negishi cross‐coupling reactions.…”

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Facile Access to Challenging ortho‐Terphenyls via Merging Two Multi‐Step Domino Reactions in One‐Pot: A Joint Experimental/Theoretical Study

et al. 2019

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ortho‐Terphenyls are of high interest for medicinal chemistry and materials science, but they are difficult to access. Herein, we demonstrate a straightforward and sustainable synthesis of highly functionalized ortho‐terphenyls via joining an organocatalyzed two‐step domino reaction (Knoevenagel/vinylogous Michael) with a DABCO/CuBr2 co‐catalyzed three‐step domino reaction (cyclization/tautomerization/aromatization) in a one‐pot process. Overcoming necessity to isolate intermediate products leads to a reduction of energy, costs and waste for a broad scope of reactions. DFT calculations have been performed to investigate the thermodynamics of this one‐pot process towards ortho‐terphenyls and to study the reaction profile of the vinylogous Michael reaction under inclusion of solvent effects. Role of London dispersion forces in this transformation has been elucidated. It is shown that reaction kinetics and thermodynamics are slightly influenced by dispersion interactions. Furthermore, the addition of dispersion energy donors leads to small changes of reaction energies in some cases.

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Dien‐Synthesen arylierter Diene. Die Dimerisation von β‐Phenyl‐butadien

Cited by 32 publications

References 12 publications

Rearrangements in Lewis acid catalyzed Diels-Alder reactions. Route to substituted bicyclo[2.2.1]heptanones

Rearrangements in Lewis acid catalyzed Diels-Alder reactions. Route to substituted bicyclo[2.2.1]heptanones

A Novel and Facile Synthesis of 2,3-Diphenylbuta-1,3-diene

Facile Access to Challenging ortho‐Terphenyls via Merging Two Multi‐Step Domino Reactions in One‐Pot: A Joint Experimental/Theoretical Study

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