Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate

Wang, Chengqiang; Feng, Chao

doi:10.1002/ange.201708505

Cited by 14 publications

(3 citation statements)

References 78 publications

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“…This result indicated that pathway Bmight be more favorable, and is also consistent with previous reports by the groups of Feng [12] and Tanaka. This result indicated that pathway Bmight be more favorable, and is also consistent with previous reports by the groups of Feng [12] and Tanaka.…”

supporting

confidence: 92%

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

Wang

et al. 2019

Angew Chem Int Ed

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supporting

confidence: 92%

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

Wang

et al. 2019

Angew Chem Int Ed

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“…To determine the order of the Lossen rearrangement and the carbene migratory insertion, 1na was subjected to the standard reaction condition with several nucleophiles such as methanol and aniline instead of 2a,which, however, resulted in no Lossen rearrangement/nucleophilic addition product, but only in recovery of the starting materials (Scheme 5E). This result indicated that pathway Bmight be more favorable, and is also consistent with previous reports by the groups of Feng [12] and Tanaka. [10d] Based on the experimental results,atentative mechanism for the reaction is proposed (Scheme 6).…”

Section: Angewandte Chemiementioning

confidence: 99%

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

Dai

et al. 2019

Angewandte Chemie

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Ar hodium(III)-catalyzed domino annulation of simple olefins with diazo oxindoles to give spirooxindole pyrrolone products is described. This reaction can be formally viewed as the result of an anomalous tandem CÀHactivation, carbene insertion, Lossen rearrangement, and an ucleophilic addition process.T he potential utility of this reaction was further demonstrated by the late-stage diversification of drug molecules.Spirooxindole frameworks can be found in al arge number of natural or synthetic compounds with potent bioactivity profiles. [1] Thei ntroduction of spiro-containing systems not only influences the biological activity and physicochemical property of the parent compounds in drug discovery programs,but also increases structural novelty for patentability. [2] Nowadays,c ommon methods for the synthesis of spirooxindoles include [3+ +2] cycloadditions, [3] Mannich reactions, [4] rearrangements of strained rings, [5] and nucleophilic substitution. [6] However,many of these existing methods suffer from certain limitations,s uch as complicated starting materials, multistep strategies,n arrow substrate scopes,o rh arsh reaction conditions.G reat attention is still devoted to the development of novel and simple methods for the synthesis of such compounds.As C À Ha ctivation has shown great potential in the generation of complex skeletons in as imple and atomeconomic fashion from readily available precursors, [7] the development of an elegant one-step C(sp 2 )ÀHf unctionalization reaction for the construction of spirooxindoles has attracted the attention of synthetic chemists.Aseries of palladium-catalyzed spirocyclizations involving sequential carbopalladation, intramolecular C À Ha ctivation, and electrophile insertion have been achieved. [8] Alternatively,aRh IIIcatalyzed annulation of N-pivaloyloxy benzamides with diazo compounds to provide isoindolones has also been reported [9] (Scheme 1A). Like the CÀHa ctivation of arenes,a lkene CÀHa ctivation has also received significant attention in recent years. [10] Moreover,m ultisubstituted spirooxindole pyrrolones could be synthesized by C À Ha ctivation of simple olefins.H erein, we described aR h III -catalyzed domino annulation of N-pivaloyloxy acrylamides with diazo oxindoles to give spirooxindole pyrrolone products in good yields and with excellent regioselectivities (Scheme 1B). This reaction could proceed through aC ÀHa ctivation, carbene insertion, Lossen rearrangement, and nucleophilic addition sequence.T he potential utility of this method in late-stage diversification for drug discovery was exemplified by the direct introduction of spirooxindole pyrrolone skeletons into the drug compounds pentoxifylline,e ndofolliculina, and pregnenolone.Fort he construction of the spirooxindole pyrrolone architecture,w eb egan our investigation by choosing N-pivaloyloxy methacrylamide 1a and diazooxindole 2a as the substrates.Inthe presence of 2.5 mol %[RhCp*Cl 2 ] 2 and 0.2 equiv of Cs 2 CO 3 in MeCN,the expected compound 3 was not formed. However,t he rearranged ...

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“…In recent years, the −NHOR-tethered substrate has also been found to proceed with an unusual Lossen rearrangement triggered by a rhodium-catalyzed C–H activation . In 2017, Feng’s group disclosed a Rh(III)-catalyzed C–H activation/Lossen rearrangement of N -pivaloyloxybenzamides with internal alkynes to afford alkenylation products . Thereafter, Rh(III)-catalyzed C–H activation/Lossen rearrangement/[3 + 2] annulation and [4 + 2] annulation cascades (Scheme c) were independently developed by Tanaka and Osipov et al ., providing highly functionalized indole- and quinolone-containing amino acid derivatives.…”

mentioning

confidence: 99%

[4 + 2] Cyclization or Lossen Rearrangement: Rhodium-Catalyzed Divergent Synthesis of Carboline Derivatives with Anticancer Activity

Lv,

Zheng,

Xiao

et al. 2024

Org. Lett.

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Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate

Cited by 14 publications

References 78 publications

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)‐Catalyzed C−H Activation/Carbene Insertion/Lossen Rearrangement Sequence

[4 + 2] Cyclization or Lossen Rearrangement: Rhodium-Catalyzed Divergent Synthesis of Carboline Derivatives with Anticancer Activity

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