Copper-Catalyzed Oxidative Decarboxylative Couplings of Sulfoximines and Aryl Propiolic Acids

Priebbenow, Daniel L.; Becker, P.; Bolm, Carsten

doi:10.1021/ol403106e

Cited by 99 publications

(28 citation statements)

References 46 publications

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“…[18c] Under the optimized reaction conditions,ah ost of alkyl amine nucleophiles and electron-poor aryl acetic acids can be decarboxylatively cross-coupled ( Figure 4). Both cyclic and acyclics econdary amines,i na ddition to primary amines, undergo benzylation in moderate to excellent yields (2,(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[6c] Cu-catalyzed C(sp) À N decarboxylative alkynylation has been limited to weakly nucleophilic NH partners (carbamates,l actams,i ndoles, sulfoximines). [8] ForC (sp 3 )-carboxylate amination, reports are limited to decarboxylative condensation processes that ultimately generate C(sp 2 ) À Nu nits in arylquinazolines, [9] or intramolecular decarboxylative aminations that require picolyl amine directing groups. [10] Existing methods for intermolecular decarboxylative cross-coupling of carboxylic acids and NH nucleophiles to generate C(sp 3 )ÀNb onds require stoichiometric activation of the acid.…”

Section: Introductionmentioning

confidence: 99%

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Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids

et al. 2019

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The decarboxylative coupling of a carboxylic acid with an amine nucleophile provides an alternative to the substitution of traditional organohalide coupling partners. Benzoic and alkynyl acids may be directly aminated by oxidative catalysis. In contrast, methods for intermolecular alkyl carboxylic acid to amine conversion, including amidate rearrangements and photoredox‐promoted approaches, require stoichiometric activation of the acid unit to generate isocyanate or radical intermediates. Reported here is a process for the direct chemoselective decarboxylative amination of electron‐poor arylacetates by oxidative Cu catalysis. The reaction proceeds at (or near) room temperature, uses native carboxylic acid starting materials, and is compatible with protic, electrophilic, and other potentially complicating functionality. Mechanistic studies support a pathway in which ionic decarboxylation of the acid generates a benzylic nucleophile which is aminated in a Chan–Evans–Lam‐type process.

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Section: Angewandte Chemiementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids

et al. 2019

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“…98,99 N-Alkynylated sulfoximines 29 are structurally related to ynamides and recent studies by Bolm and coworkers have shown their greater reactivity in various transformations. [100][101][102][103] In particular, in what concerns the chemistry covered here, these highly activated alkynes are prone to undergo the regioselective catalystfree addition of carboxylic acids under remarkably mild reaction conditions (even at -20 °C). As shown in Scheme 15, performing the reactions in THF at r.t., different enol esters 30 could be synthesized in moderate to gold yields, in only 1 h, and with excellent stereoselectivities.…”

Section: Metal-free Reactionsmentioning

confidence: 99%

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

González-Liste¹,

Francos²,

García‐Garrido³

et al. 2017

Arkivoc

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The intermolecular addition of carboxylic acids to alkynes is one of the most straightforward and atomeconomical methods currently available for the preparation of synthetically useful enol esters. However, the vast majority of works have focused on the use of terminal alkynes, substrates much more reactive than their corresponding internal counterparts. In fact, efficient and general protocols for hydro-oxycarbonylation of internal alkynes have only seen the light in recent years. In the present review article an overview of the progress made in the field is given. Catalytic reactions promoted by ruthenium, palladium, silver and gold complexes/salts, along with some specific metal-free protocols, are covered.

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“…7 Since then, significant progress has been made by us and other groups. 8 A variety of substrates have been successfully employed as coupling partners, such as benzyl halide, 9 C-H activated heteroarenes, 10 organoboranes, 11 amides, 12 and organophosphorus 13 and organosulfur 14 compounds. Very recently, we reported a decarboxylative coupling reaction with organosilane using a nickel catalyst, which provided the diaryl alkyne in moderate to good yields.…”

mentioning

confidence: 99%