An Iterative Method for the Synthesis of Symmetric Polyynes

DeCicco, Racquel C.; Black, Allison; Li, Lei; Goroff, Nancy S.

doi:10.1002/ejoc.201200442

Cited by 29 publications

(34 citation statements)

References 52 publications

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“…Another interesting reactivity of 1‐halopolyynes is a unique single‐crystal‐to‐single‐crystal topochemical dimerization 22. Moreover, 1‐halopolyynes are used in the iterative synthesis of longer polyynes by Negishi23 or Stille reaction18b or in the synthesis of butadiyne‐substituted pyrroles 24. Despite sparse experimental data on their synthesis, modern computational studies of halogen end‐capped polyynes are fairly numerous 25…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Long, Palladium End‐Capped Polyynes through the Use of Asymmetric 1‐Iodopolyynes

Pigulski

Gulia

Szafert

2015

Chemistry A European J

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The synthesis of a unique series of long, asymmetric 1-iodopolyynes (1-Cn I and 2-Cn I) with the sp-hybridized carbon chain up to a decapentayne is reported. These compounds were then used as substrates in reactions with Pd(PPh3 )4 leading to another series of palladium end-capped polyynes, which were unstable in solution. Organometallic octatetraynes 1-C8 [Pd]I, 2-C8 [Pd]I, and decapentayne 1-C10 [Pd]I are palladium end-capped polyyne compounds with the longest carbon chains reported so far. All the complexes as well as their organic precursors were fully characterized by NMR, HRMS(ESI), IR, TGA-DTA, and UV/Vis techniques, and the X-ray crystal structures of two silyl-protected precursors and one palladium complex are presented. The synthetic approach for palladium species is envisioned as a general route for the synthesis of labile organometallic polyynes.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Long, Palladium End‐Capped Polyynes through the Use of Asymmetric 1‐Iodopolyynes

Pigulski

Gulia

Szafert

2015

Chemistry A European J

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“…Single-crystal X-ray data were collected at 120(2) K on a Bruker SMART CCD 6000 (fine-focus sealed tube, graphite-monochromator). 26 A Schlenk flask was charged with ICCCCSiMe 3 (0.10 g, 0.40 mmol), HCCCCSiMe 3 (90.0 L, 0.07 g, 0.60 mmol), Pd(PPh 3 ) 4 (6.8 mg, 0.06 mmol) and CuI (1 mg, 0.06 mmol) in a degassed solution of NEt 3 (10 mL). The yellow solution was stirred overnight at room temperature, under argon.…”

Section: General Detailsmentioning

confidence: 99%

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

et al. 2015

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Citation for published item:wil nD h vid gF nd elEyw ediD yd y eF nd yerthelD w rieEghristine nd w rqu¡ esEqonz¡ lezD nti go nd frookeD i h rd tF nd fry eD w rtin F nd ge D il r nd perrerD t ime nd rigginsD imon tF nd v m ertD golin tF nd vowD ul tF nd solt w nriqueD h vid nd w rtinD nti go nd xi holsD i h rd tF nd hw rz herD lther nd q r ¡ % E u¡ rezD ¡ % tor wF @PHITA 9 olvent dependen e of the single mole ule ondu t n e of oligoyneE sed mole ul r wiresF9D tourn l of physi l hemistry gFD IPH @PWAF ppF ISTTTEISTURF Further information on publisher's website:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in The Journal of Physical Chemistry C, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acs.jpcc.5b08877. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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“…[157,160] Moreover, deprotective iodination under basic conditions reported by Sticha gave good yield for 1,4-diiodobutadiyne and 1,6-diiodohexatriyne (Table 6). [136,157,160] As shown, monoiodopolyynes are significantly more thermally stable than diiodo homologs. by a nucleophilic attack of OHon the triple bond pathway) when it is applied for the synthesis of long chain 1-halopolyynes.…”

Section: Transformations Of 1-halopolyynesmentioning

confidence: 87%

“…by a nucleophilic attack of OHon the triple bond pathway) when it is applied for the synthesis of long chain 1-halopolyynes. [160,163,164] Efficiency and mild conditions of desililative bromination reaction allow to apply it for the synthesis of the solid state library of bromopolyynes (Scheme 39). [139] Decomposition temperature is a convenient parameter to compare relative stability of 1-halopolyynes.…”

Section: Transformations Of 1-halopolyynesmentioning

confidence: 99%

Reactivity of Polyynes: Complex Molecules from Simple Carbon Rods

2019

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Polyynes are linear carbon rods that may be regarded as models of carbyne – still elusive linear allotropic form of carbon. This microreview addresses the use of polyynes as synthetic precursors of complex organic and organometallic compounds. Application of such unusual molecules as starting materials for various chemical transformations leads to products which often are not easily accessible using “traditional“ approaches. Polyynes may for instance be used in the synthesis of molecular wires, materials possessing high nonlinear optical response, complex donor–acceptor systems, solvatochromic fluorescent dyes or natural products. The most significant challenge here is to control the regioselectivity of a transformation of such linear sp‐hybridized carbon chains. The impact of steric and electronic properties of reagents on the reaction pattern is hence highly important and will be discussed. Moreover, the transformations of end‐groups will also be addressed since their reactivity might very often be different than that of acetylenes.

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An Iterative Method for the Synthesis of Symmetric Polyynes

Cited by 29 publications

References 52 publications

Synthesis of Long, Palladium End‐Capped Polyynes through the Use of Asymmetric 1‐Iodopolyynes

Synthesis of Long, Palladium End‐Capped Polyynes through the Use of Asymmetric 1‐Iodopolyynes

Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires

Reactivity of Polyynes: Complex Molecules from Simple Carbon Rods

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