Biaryls, Stilbenes, Benzo [<i>c</i>]cinnolines, and Dibenz [<i>c,mn</i>] acridines from Sulfonamides

Waldau, Eckart; Pütter, Rolf

doi:10.1002/anie.197208261

Cited by 16 publications

(14 citation statements)

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“…9 Gravimetric analysis of the extruded sulfur dioxide, via the formation of BaSO 4 , was exploited base-H + as a convenient method for measuring reaction rates in kinetic studies of these reactions. 15 The tandem Truce-Smiles rearrangement -sulfur dioxide extrusion [34][35][36][37][38][39][40][41][42][43] sequence is likely a common combination, because the sulfonyl group is a useful substituent on the migrating aryl ring that can serve as both an activating group for stabilizing the Meisenheimer adduct by withdrawing electron density through an inductive effect and as a competent leaving group. This is discussed further in section 4.1.…”

Section: Tandem Reactionsmentioning

confidence: 99%

“…An interesting extension of the S N Ar mechanism for the TruceSmiles rearrangement has been the reported 35 vinylogous version of the reaction. An example of this reaction is shown in Scheme 8.…”

Section: Vinylogous Reactionsmentioning

confidence: 99%

“…35 The report also provides an account of the rearrangement of numerous non-vinylogous substrates. The apparent preference of the carbanion nucleophile to attack in a vinylogous manner as opposed to at the conventional S N Ar ipso carbon electrophile may be influenced by the apparent preference of TruceSmiles rearrangement reactions to proceed via 5-membered spirocyclic Meisenheimer adducts as opposed to the alternative 7-membered adduct.…”

Section: Vinylogous Reactionsmentioning

confidence: 99%

“…Beyond N-heterocycles, the scope of the Truce-Smiles rearrangement has successfully been expanded to include substrates that feature sulfur-containing N-heterocycles as the migrating aryl ring such as benzothiazole, 35 thienopyridine, 97 and benzothiophene. 23 Examples of each of these substrates (92, 94, and 97, respectively) are shown in Scheme 30.…”

Section: Pyridine and Related Aza-aromaticsmentioning

confidence: 99%

“…Scheme 30. Example of successful rearrangement of benzothiazole, 35 thienopyridine, 97 and benzothiophene 23 substrates. This section of the review has illustrated the scattered and adventitious nature of the literature pertaining to the Truce-Smiles rearrangement of heterocyclic substrates.…”

Section: Pyridine and Related Aza-aromaticsmentioning

confidence: 99%

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The Truce–Smiles rearrangement and related reactions: a review

2017

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Abstract:The Truce-Smiles rearrangement is an X ¡ C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce-Smiles rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

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Section: Tandem Reactionsmentioning

confidence: 99%

Section: Vinylogous Reactionsmentioning

confidence: 99%

Section: Vinylogous Reactionsmentioning

confidence: 99%

Section: Pyridine and Related Aza-aromaticsmentioning

confidence: 99%

Section: Pyridine and Related Aza-aromaticsmentioning

confidence: 99%

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The Truce–Smiles rearrangement and related reactions: a review

2017

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Metal Free Bi(hetero)aryl Synthesis: A Benzyne Truce–Smiles Rearrangement

2016

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An ew benzyne transformation is described that affords versatile biaryl structures without recourse to transition-metal catalysis or stoichiometric amounts of organometallic building blocks.Aryl sulfonamides add to benzyne upon fluoride activation, and then undergo an aryl Truce-Smiles rearrangement to affordb iaryls with sulfur dioxide extrusion. The reaction proceeds under simple reaction conditions and has excellent scope for the synthesis of sterically hindered atropisomeric biaryl amines.The biaryl motif is fundamental to chemistry,a si ti sw idely represented in natural products,m aterials,p harmaceuticals, and agrochemicals.Synthesis of these ubiquitous structures is often carried out using transition-metal catalysis and stoichiometric amounts of metallated arenes,w hich enable the coupling of two sp 2 -carbon centers via organometallic intermediates.[1] Thedrive for sustainable synthetic methods which avoid both the use of expensive and scarce transition metals, and the separate preparation of aryl metal reactants,h as stimulated efforts to develop metal-free biaryl syntheses. [2][3][4] Achieving the controlled union of two arene fragments without organometallic assistance is very challenging,a nd current methods are often forced to employ harsh reaction conditions and/or operationally complex protocols.R ecent examples include UV photochemistry to generate aryl cations from electron-rich arenes, [3a] oxidative coupling of electronrich arenes in the presence of strong Lewis acids, [3b-d] and base-mediated coupling of aryl iodides with simple arenes through electron transfer.[4] This latter approach has received significant attention in recent literature and uses the combination of an alkali metal base and an electron-rich ligand to generate aryl radicals through as ingle-electron transfer. Subsequent S Ar Hs ubstitution and oxidation lead to biaryl formation (Scheme 1a). Them ethod is impressively simple, but requires high temperatures,u pt o2 0-fold excess of the arene coupling partner,and produces regioisomeric mixtures of substituted biaryls.T he discovery of am ild, metal-free biaryl synthesis with broad substrate scope would therefore be as ignificant development in the field.We were interested in applying the reactive intermediate benzyne to this problem. Arynes are versatile intermediates in biaryl synthesis,with their addition to aryl organometallics being awell-described method, known since the earliest days of aryne chemistry. [5,6] Cross-coupling with simple arenes, however, in the absence of organometallic species,has rarely been reported as asynthetic method. [7] Given that arynes undergo smooth addition to heteroatom nucleophiles, [8] we wondered if this feature could be exploited in am etal-free biaryl synthesis through addition/ rearrangement chemistry.O ur synthetic plan is set out in Scheme 1b.S tarting with readily available aryl sulfonamides (1), addition of abenzyne [generated from a2-trimethylsilyl-(phenyl) triflate precursor upon treatment with fluoride] should give the ...

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Metal‐Free Intermolecular Aminoarylation of Alkynes

2017

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A metal‐free aminoarylation of internal alkynes is described, yielding tetrasubstituted enaminoates. The transformation proceeds in good to excellent yields through a tandem conjugate addition/Smiles rearrangement involving aryl and heteroaryl sulfonamides. Substrate scope is very broad under simple, user‐friendly conditions, and the reaction can be used to easily access biologically active phenethylamine derivatives.

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Biaryls, Stilbenes, Benzo [c]cinnolines, and Dibenz [c,mn] acridines from Sulfonamides

Cited by 16 publications

References 0 publications

The Truce–Smiles rearrangement and related reactions: a review

The Truce–Smiles rearrangement and related reactions: a review

Metal Free Bi(hetero)aryl Synthesis: A Benzyne Truce–Smiles Rearrangement

Metal‐Free Intermolecular Aminoarylation of Alkynes

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