2-Vinyl-1,3-butadiene<sup>1</sup>

Blomquist, A. T.; Verdol, Joseph A.

doi:10.1021/ja01606a025

Cited by 71 publications

(29 citation statements)

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“…Our first attempt to prepare this C 7 H 8 hydrocarbon was modeled on the classic synthesis of [3]dendralene (1, n = 1) by Blomquist and Verdol, [17] in which the two terminal double bonds are generated from 1,5-diacetoxy-3-methylenepentane (33, Scheme 5) by acetate pyrolysis in the last step. Application of this sequence to the synthesis of 3 required the preparation of the allene diacetate 38.…”

Section: -Vinylpenta-124-triene (3 11-divinylallene)mentioning

confidence: 99%

The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

2011

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The cross‐conjugated allenes (“allenic dendralenes”) 2‐allenylbuta‐1,3‐diene (2), 1,1‐divinylallene (3, prepared here as the methyl derivative 49), and 1,1‐diallenylethene (4) are prepared either by SN2′‐substitution processes from appropriate allenic or acetylenic precursors or by base‐catalyzed isomerizations of propargylic substrates. Thermal elimination/isomerization routes to these highly unsaturated hydrocarbons require reaction conditions under which these allenes undergo secondary transformations. The new oligoolefins, the structures of which have been calculated by MP2 methods, are interesting substrates for addition and isomerization reactions.

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Section: -Vinylpenta-124-triene (3 11-divinylallene)mentioning

confidence: 99%

The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

2011

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“…[2] They have found numerous applications for rapid access to polycyclic frameworks, [3] and have also been engaged in targeted syntheses of natural products, such as vinigrol [4] or triptolide. [5] Since the early report of Blomquist and Verdol, [6] several routes have been developed to synthesize [7-9] More recently, cross-conjugated dioxatrienes 3 with two heteroatoms were synthesized and were engaged in sequential reactions to provide pyran-fused aza-and thia-heterocycles. [10,11] In parallel, Pi and Bodwell described normal and inverse electron demand Diels-Alder reactions of dienes 4, [12] while, more recently, Spino and Perreault have intensively investigated a very elegant intramolecular strategy to construct the quassinoid framework through tandem cycloadditions involving cyclic compounds 5 (Figure 1).…”

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confidence: 99%

Boron‐ and Silicon‐Substituted [3]‐1‐Heterodendralenes as Versatile Building Blocks for the Rapid Construction of Polycyclic Architectures

Tripoteau

Verdelet

Hercouet

et al. 2011

Chemistry A European J

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“…[3,4] Until the synthesis of den dralenes via crosscoupling reactions was reported, a majority of the dendralenes were prepared by the thermal decomposition of precursors. [5][6][7] However, in recent years, various [n]dendralenes, up to [8]dendralenes, have been synthesized in high yield via the crosscoupling reaction of 1,3butadiene2ylmagnesium chlo ride with appropriate halogenated compounds. [8] Among various [n]dendralenes, the smallest dendralene [3]dendralene was syn thesized in 1955.…”

Section: Introductionmentioning

confidence: 99%

“…[8] Among various [n]dendralenes, the smallest dendralene [3]dendralene was syn thesized in 1955. [9] Although various [3]dendralene derivatives have been systematically synthesized since that report, few www.advancedsciencenews.com www.mcp-journal. de structure is of considerable interest because every carboncarbon double bond can participate in polymerization.…”

Section: Introductionmentioning

confidence: 99%

Anionic Polymerization of 2‐Hexyl[3]dendralene

Takamura

Takenaka

Toda

et al. 2017

Macro Chemistry & Physics

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studies have reported the addition poly merization of [3]dendralene derivatives. [10] Previously, our group has reported the anionic polymerization of 2phenyl [3]den dralene (P3D) and 2(4methoxyphenyl) [3]dendralene (MP3D). [11] In both cases, anionic polymerization smoothly pro ceeds in polar solvents at low tempera ture, affording a polymer with a narrow mole cular weight distribution and a conjugate addition chain structure com prising conjugated carbon-carbon double bonds in the polymer chain, as shown in Scheme 1. However, a bimodal molecular weight distribution was observed when the poly merization mixture was stand still for a long duration after the monomer was completely consumed, presumably because of the nucleophilic addition of the propagating carbanion to the conjugated double bond in the polymer chain, as shown in Scheme 2. Hence, it is crucial to select the polymerization conditions to obtain polymers with controlled chain structures.This side reactions, nucleophilic addition of propagating chain end to the polymer chain, can also be prevented via the lowering of the reactivity of conjugated carbon-carbon double bond in the polymer chain by changing the double bond sub stituent. The carbon-carbon double bond in the polymer chain is conjugated by the phenyl group (Scheme 2), which facilitates easier nucleophilic attack of the propagating carbanion to the double bond compared with the case of an unsubstituted double bond. Hence, the polymerization behavior of [3]den dralene derivatives with a nonconjugating substituent on the C2 carbon of the [3]dendralene framework is interesting. Hence, 2(nhexyl)[3]dendralene (H3D) is selected as a candi date to compare the effect of substituents on its polymerization behavior with that of P3D.Notably, the microstructure of the resulting polymers is also interesting. As expected, the 2substituted[3]dendralene Dendralene In this study, the polymerization behavior of 2-hexyl[3]dendralene (H3D), which is an alkyl-group-derived [3]dendralene, is examined. The polymerization of H3D in tetrahydrofuran (THF) at −78 °C with potassium naphthalenide as the initiator affords poly(H3D) with a narrow molecular weight distribution, although a small shoulder peak is observed at a high molecular weight even before the monomer is completely consumed. The molecular weight distribution of poly(H3D) prepared in heptane is broader than that prepared in THF, indicating that the nucleophilic addition of a propagating carbanion to the carbon-carbon double bond in the polymer chain occurs in addition to polymerization. Furthermore, the microstructure of poly(H3D) is investigated by NMR. Signals corresponding to the conjugate addition structure, that is, 1,4-and 4,6-structures, are exclusively observed. Poly(H3D) prepared in heptane contains a higher content of the 4,6-structures compared with those prepared in THF.

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2-Vinyl-1,3-butadiene¹

Cited by 71 publications

References 0 publications

The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

Boron‐ and Silicon‐Substituted [3]‐1‐Heterodendralenes as Versatile Building Blocks for the Rapid Construction of Polycyclic Architectures

Anionic Polymerization of 2‐Hexyl[3]dendralene

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2-Vinyl-1,3-butadiene1

Cited by 71 publications

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The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

The Preparation and Structures of Several Cross‐Conjugated Allenes (“Allenic Dendralenes”)

Boron‐ and Silicon‐Substituted [3]‐1‐Heterodendralenes as Versatile Building Blocks for the Rapid Construction of Polycyclic Architectures

Anionic Polymerization of 2‐Hexyl[3]dendralene

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2-Vinyl-1,3-butadiene¹