Nucleophilic Coupling with Arynes

Kessar, S. V.

doi:10.1016/b978-0-08-052349-1.00101-3

Cited by 82 publications

(27 citation statements)

References 164 publications

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“…This has been explained by several models. In the Charge-Controlled Model , 11 the X group polarizes the triple bond, and nucleophilic addition occurs at the site of greatest positive charge. 12 A related model, based on Natural Bond Orbital (NBO) electron densities of in-plane π-orbitals, has been advocated by Ikawa, Akai, and co-workers.…”

Section: Introductionmentioning

confidence: 99%

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

et al. 2014

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The distortion/interaction model has been used to explain and predict reactivity in a variety of reactions where more common explanations, such as steric and electronic factors, do not suffice. This model has also provided new fundamental insight into regioselectivity trends in reactions of unsymmetrical arynes, which in turn, has fueled advances in aryne methodology and natural product synthesis. This article describes a systematic experimental and computational study of one particularly important class of arynes, 3-halobenzynes. 3-Halobenzynes are useful synthetic building blocks whose regioselectivities have been explained by several different models over the past few decades. Our efforts show that aryne distortion, rather than steric factors or charge distribution, are responsible for the regioselectivities observed in 3-haloaryne trapping experiments. We also demonstrate the synthetic utility of 3-halobenzynes for the efficient synthesis of functionalized heterocycles, using a tandem aryne trapping/cross-coupling sequence involving 3-chlorobenzyne.

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Section: Introductionmentioning

confidence: 99%

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

et al. 2014

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“…Moreover, such pericyclic processes have also been applied to the synthesis of pharmacophores [8] and other interesting classes of substances. [9] Along with pericyclic reactions, in situ generated arynes have also been shown to act as efficient acceptors in reactions with various nucleophiles, [10] in "addition/protonation" sequences, [11] and in "addition/trapping" [12] to yield the corresponding mono-or disubstituted benzene derivatives. One major challenge in these sequences is the control of regioselectivity in the initial addition step.…”

Section: Introductionmentioning

confidence: 99%

2,2′‐Bis‐substituted Biphenyls by the Addition of Nucleophiles to Benzyne Followed by In Situ Oxidative Homocoupling

2015

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The paper describes the addition of Mg‐anilides and ‐thiolates to in situ generated benzyne with subsequent oxidative homocoupling of the adducts to give 2,2′‐bis‐substituted biphenyls in a one‐pot process. Oxidative C–C bond formation was best achieved with a Cu catalyst using O2 as oxidant. The sequence comprises two C–X and one C–C bond formation and the products were obtained in moderate yields. Some of the 2,2′‐bis‐substituted biphenyls have been characterized by X‐ray analysis.

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“…The use of arynes as the highly reactive intermediates in organic synthesis has attracted substantial attention [20,21,22,23,24,25,26,27]. The recent dramatic progress in aryne-based chemistry is summarized in the review articles [28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes

Miyabe

2015

Molecules

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Most of the synthetic approaches to the benzo-fused heterocycles containing an oxygen atom have involved the use of phenol derivatives as a starting material. This review highlights the new synthetic approaches involving the aromatic C-O bond-forming process using arynes. The insertion of arynes into the C=O bond gives the unstable intermediates, [2 + 2] cycloaddition-type adducts, which can be easily converted into a variety of oxygen atom-containing heterocycles in a single operation. In this review, the syntheses of oxygen heterocycles, such as coumarin, chromene, xanthene, dihydrobenzofuran and benzofuran derivatives, via the insertion of arynes into the C=O bond of aldehydes or formamides are summarized.

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Nucleophilic Coupling with Arynes

Cited by 82 publications

References 164 publications

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions

2,2′‐Bis‐substituted Biphenyls by the Addition of Nucleophiles to Benzyne Followed by In Situ Oxidative Homocoupling

Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes

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