The Mechanism of Reaction Between Thionylaniline and Organomagnesium Halides

Gilman, Henry; Morris, Harry

doi:10.1021/ja01420a025

Cited by 32 publications

(10 citation statements)

References 3 publications

(4 reference statements)

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“…[10] However,s ulfinamides are not easily accessible and have limited commercial availability,a nd are typically prepared from sulfinyl chlorides,a ccessible via oxidation of thiols or disulfides,o rr eduction of moisturesensitive sulfonyl chlorides. 3), chlorination of the resultant anionic sulfinamide species [13] to generate as ulfonimidoyl chloride (3 ! Ther esulting one-pot, three-component reaction sequence would involve combination of the sulfinylamine with an organometallic reagent (2 !…”

Section: Sulfonamideshavearichhistoryinmedicinalchemistryandmentioning

confidence: 99%

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One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

2017

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Sulfonimidamides are increasingly important molecules in medicinal chemistry and agrochemistry, but their preparation requires lengthy synthetic sequences, which has likely limited their use. We describe a one-pot de novo synthesis of sulfonimidamides from widely available organometallic reagents and amines. This convenient and efficient process uses a stable sulfinylamine reagent, N-sulfinyltritylamine (TrNSO), available in one step on 10 gram scale, as a linchpin. In contrast to classical approaches starting from thiols or their derivatives, our TrNSO-based approach facilitates the rapid assembly of the three reaction components into a variety of differentially substituted sulfonimidamides containing medicinally relevant moieties, including pyridines and indoles. Analogues of the sulfonamide-containing COX-2 inhibitor Celecoxib were prepared and evaluated.

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Section: Sulfonamideshavearichhistoryinmedicinalchemistryandmentioning

confidence: 99%

“…Organolithium reagent 11 was obtained from the corresponding bromide and employed in the synthesis of three sulfonimidamides (12)(13)(14). Organolithium reagent 11 was obtained from the corresponding bromide and employed in the synthesis of three sulfonimidamides (12)(13)(14).…”

Section: Angewandte Chemiementioning

confidence: 99%

One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

2017

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“…Ther esulting one-pot, three-component reaction sequence would involve combination of the sulfinylamine with an organometallic reagent (2 ! 3), chlorination of the resultant anionic sulfinamide species [13] to generate as ulfonimidoyl chloride (3 ! 4), [7c] and then combination with an amine to afford an N-substituted sulfonimidamide (4 !…”

Section: Sulfonamideshavearichhistoryinmedicinalchemistryandmentioning

confidence: 99%

“…Having developed ac onvenient method to prepare sulfonimidamides,w ew ished to investigate its suitability for preparing complex, drug-like molecules.Wetherefore elected to investigate the preparation of sulfonimidamide analogues of the sulfonamide-containing non-steroidal anti-inflammatory drug (NSAID) Celecoxib (Scheme 4). Organolithium reagent 11 was obtained from the corresponding bromide and employed in the synthesis of three sulfonimidamides (12)(13)(14). Possibilities for further functionalization on these complex structures were explored; N-alkylation of 12 with methyl iodide proceeded quantitatively (15), while N-arylation via ap alladium-catalyzed cross-coupling was also successful (16).…”

Section: Angewandte Chemiementioning

confidence: 99%

One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

2017

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Sulfonimidamides are increasingly important molecules in medicinal chemistry and agrochemistry,b ut their preparation requires lengthy synthetic sequences,w hich has likely limited their use.Wedescribe aone-pot de novo synthesis of sulfonimidamides from widely available organometallic reagents and amines.This convenient and efficient process uses astable sulfinylamine reagent, N-sulfinyltritylamine (TrNSO), available in one step on 10 gram scale,asalinchpin. In contrast to classical approaches starting from thiols or their derivatives, our TrNSO-based approach facilitates the rapid assembly of the three reaction components into av ariety of differentially substituted sulfonimidamides containing medicinally relevant moieties,i ncluding pyridines and indoles.A nalogues of the sulfonamide-containing COX-2 inhibitor Celecoxib were prepared and evaluated. Scheme 1. a) At ypical linear synthesis of sulfonimidamides via the intermediacy of unstable sulfinyl chlorides.b )This work:aone-pot sulfinylamine-based synthesis of sulfonimidamides.

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“…[11] Our group carried out computational (Natural Bond Orbital) studies on the structure of the sulfinylamine PhÀ OÀ N=S=O and found that favourable donation of the nitrogen lone pair into the SÀ O σ* orbital, and of the sulfur lone pair into the NÀ O σ* orbital, help to stabilise the (Z)conformation relative to the (E)-conformation. [12] The fundamental chemistry of sulfinylamines including Diels-Alder cycloadditions [13] and attack of various nucleophiles such as alcohols, amines and Grignard reagents [14] (Scheme 2) has been covered in previous reviews and so will not be described in detail here. [3] This Minireview will summarise advances principally from the last decade.…”

Section: Introductionmentioning

confidence: 99%

Rediscovering Sulfinylamines as Reagents for Organic Synthesis

Davies

Willis

2021

Chemistry A European J

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Sulfinylamines (RÀ N=S=O), monoaza analogues of sulfur dioxide, have been known for well over a century, and their reactivity as sulfur electrophiles and in Diels-Alder reactions is well-established. However, they have only rarely been used in organic synthesis in recent decades despite the increasing prominence of compounds containing N=S=O functionality, such as sulfoximines and sulfonimidamides. This Minireview aims to bring wider visibility to the unique chemistry enabled by this class of compounds. We focus on advances from the last 10 years, including the first examples of their use in the one-pot syntheses of sulfoximines and sulfonimidamides. Also covered are the reactions of sulfinylamines with carbon-centred radicals, their use for formation of heterocycles through cycloadditions, and catalytic enantioselective allylic oxidation of alkenes via a hetero-ene reaction. These examples highlight the different reactivity modes of sulfinylamines and their underappreciated potential for forming molecules which contain high-or low-valent sulfur, or even no sulfur at all.

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The Mechanism of Reaction Between Thionylaniline and Organomagnesium Halides

Cited by 32 publications

References 3 publications

One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

One‐Pot, Three‐Component Sulfonimidamide Synthesis Exploiting the Sulfinylamine Reagent N‐Sulfinyltritylamine, TrNSO

Rediscovering Sulfinylamines as Reagents for Organic Synthesis

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