Synthesis of Isoquinolines from α‐Aryl Vinyl Azides and Internal Alkynes by Rh–Cu Bimetallic Cooperation

Wang, Yi‐Feng; Toh, Kah Kah; Lee, Jian‐Yuan; Chiba, Shunsuke

doi:10.1002/anie.201101009

Cited by 292 publications

(64 citation statements)

References 56 publications

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“…2 H -Azirines have been reported as intermediates in reactions involving vinyl azides as a result of the denitrogenative decomposition of the latter via vinyl nitrenes4748. As shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3–H functionalization

et al. 2017

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The quest for selective C–H functionalization reactions, able to provide new strategic opportunities for the rapid assembly of molecular complexity, represents a major focus of the chemical community. Examples of non-directed, remote Csp3–H activation to forge complex carbon frameworks remain scarce due to the kinetic stability and thus intrinsic challenge associated to the chemo-, regio- and stereoselective functionalization of aliphatic C–H bonds. Here we describe a radical-mediated, directing-group-free regioselective 1,5-hydrogen transfer of unactivated Csp3–H bonds followed by a second Csp2–H functionalization to produce, with exquisite stereoselectivity, a variety of elaborated fused ketones. This study demonstrates that aliphatic acids can be strategically harnessed as 1,2-diradical synthons and that secondary aliphatic C–H bonds can be engaged in stereoselective C–C bond-forming reactions, highlighting the potential of this protocol for target-oriented natural product and pharmaceutical synthesis.

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Section: Resultsmentioning

confidence: 99%

Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3–H functionalization

et al. 2017

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“…5 Preliminary mechanistic investigations indicated that both rhodium and copper are prerequisites for achieving catalytic activity. It was also found that benzylic radical intermediates were trapped by 2,6-di-tert-butyl-4-methylphenol (TEMPO), when it was added instead of HOAc (Scheme 12).…”

Section: Transition Metal-catalyzed Reactions Of Vinyl Azidesmentioning

confidence: 99%

“…c). 5 In the syntheses of N -heterocycles, a radical pathway might also be involved, in which α -azido radicals, 8 , generated from radical species (R · ), add to vinyl azides, to produce iminyl radicals, 9 (Scheme 1, eq. d).…”

Section: Introductionmentioning

confidence: 99%

Reactivities of vinyl azides and their recent applications in nitrogen heterocycle synthesis

DiMagno

2015

Org. Biomol. Chem.

178

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Nitrogen heterocycles are abundant in natural products and pharmaceuticals. An emerging interest among synthetic chemists is to apply vinyl azides as a pivotal three-atom synthon for the construction of structurally complex and diverse N-heterocyclic skeletons. The unique features of the azide group connected to an alkene moiety permit vinyl azides to function as electrophiles, nucleophiles, or radical acceptors; their access to diverse reaction pathways provides great opportunities to generate highly reactive intermediates with often unusual or unconventional reactivities. This tutorial review will systematically illustrate the reactivities of vinyl azides and describe recent breakthroughs in the development of new transformations that create N-heterocycles.

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“…48 While the use of sodium acetate (NaOAc) or cesium pivalate (CsOPiv) (30 mol%) as a carboxylate source did not afford any ortho carbon-hydrogen bond functionalization product (entries 1 and 2, respectively), the reaction with copper(II) acetate [Cu(OAc) 2 ] (20 mol%) at 110 °C in N,N-dimethylformamide (DMF) gave 1-methyl-3,4-diphenylisoquinoline (237) in 70% yield (entry 3). The addition of 1 equivalent of AcOH allowed for a lower reaction temperature (90 °C) and catalytic loading of [Cp*RhCl 2 ] 2 (2.5 mol%) (entries 5 and 6).…”

mentioning

confidence: 97%

“…After the extensive screening of various electrophiles, it was found that the addition of TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxyl) (2 equiv) instead of AcOH in the reaction of vinyl azides 62 and 277 with several alkynes under the [Cp*RhCl 2 ] 2 -Cu(OAc) 2 catalytic system delivered isoquinoline-TEMPO adducts and alcohols in good combined yields (Table 14). 48,52 From vinyl azide 277, a b-amino alcohol unit could be installed in the isoquinoline framework (entry 4). Although we are not certain as to the reaction mechanism of this carbonoxygen bond formation, one possibility might be the nucleophilic attack of the azaenolate carbon to a Cu(II)-TEMPO complex, which would act as an ionic electrophile.…”

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confidence: 99%

Application of Organic Azides for the Synthesis of Nitrogen-Containing Molecules

Chiba¹

2011

Synlett

Self Cite

181

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In this account, recent advances made on the reactions of several types of organic azides, such as vinyl azides, cyclic 2-azido alcohols, a-azido carbonyl compounds, towards the synthesis of nitrogen-containing molecules are described. 1 Introduction 2 Chemistry of Vinyl Azides 2.1 Thermal [3+2]-Annulation of Vinyl Azides with 1,3-Dicarbonyl Compounds 2.2 Manganese(III)-Catalyzed Formal [3+2]-Annulation with 1,3-Dicarbonyl Compounds 2.3 Manganese(III)-Mediated/Catalyzed Formal [3+3]-Annulation with Cyclopropanols 2.4 Synthesis of Isoquinolines from a-Aryl-Substituted Vinyl Azides and Internal Alkynes by Rhodium-Copper Bimetallic Cooperation 3 Chemistry of Cyclic 2-Azido Alcohols 3.1 Manganese(III)-Catalyzed Ring Expansion of 2-Azidocyclobutanols 3.2 Palladium(II)-Catalyzed Ring Expansion of Cyclic 2-Azido Alcohols 4 Chemistry of a-Azido Carbonyl Compounds 4.1 Orthogonal Synthesis of Isoindole and Isoquinoline Derivatives 4.2 Generation of Iminylcopper Species and Their Catalytic Carbon-Carbon Bond Cleavage under an Oxygen Atmosphere 4.3 Copper(II)-Catalyzed Aerobic Synthesis of Azaspirocyclohexadienones 5 Conclusion

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Synthesis of Isoquinolines from α‐Aryl Vinyl Azides and Internal Alkynes by Rh–Cu Bimetallic Cooperation

Cited by 292 publications

References 56 publications

Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3–H functionalization

Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3–H functionalization

Reactivities of vinyl azides and their recent applications in nitrogen heterocycle synthesis

Application of Organic Azides for the Synthesis of Nitrogen-Containing Molecules

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