- Oxidation of Nonactivated Anilines to Generate N-Aryl Nitrenoids
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A low-temperature, protecting-group-free oxidation of 2-substituted anilines has been developed to generate an electrophilic N-aryl nitrenoid intermediate that can engage in C-NAr bond formation to construct functionalized N-heterocycles. The exposure of 2-substituted anilines to PIFA and trifluoroacetic acid or 10 mol percent Sc(OTf)3 triggers nitrenoid formation, followed by productive and selective C-NAr and C-C bond formation to yield spirocyclic- or bicyclic 3H-indoles or benzazepinones. Our experiments demonstrate the breadth of these oxidative processes, uncover underlying fundamental elements that control selectivity, and demonstrate how the distinct reactivity patterns embedded in N-aryl nitrenoid reactive intermediates can enable access to functionalized 3H-indoles or benzazepinones.
- Deng, Tianning,Mazumdar, Wrickban,Ford, Russell L.,Jana, Navendu,Izar, Ragda,Wink, Donald J.,Driver, Tom G.
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supporting information
p. 4456 - 4463
(2020/03/05)
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- I(III)-catalyzed oxidative cyclization - Migration tandem reactions of unactivated anilines
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An I(III)-catalyzed oxidative cyclization-migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene or iodoalkane precatalyst suggests that the catalyst is present for the stereochemical determining C-N bond forming step.
- Deng, Tianning,Shi, Emily,Thomas, Elana,Driver, Tom G.
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supporting information
p. 9102 - 9106
(2020/11/13)
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- Cascade C-C and C-N Bond Formation: A Straightforward Synthesis of Phenanthridines and Fused Quinolines
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A Pd-catalyzed cascade process has been developed for the synthesis of quinoline and phenanthridine derivatives from various β-chloro α,β-unsaturated aldehydes and 2-chloroaryl aldehydes, respectively, in good to high yields. The reaction proceeds through Pd-catalyzed cascade carbon-carbon and carbon-nitrogen bond formation in a single reaction vessel. The requisite β-chloro α,β-unsaturated aldehydes were efficiently synthesized from their corresponding carbonyl compounds. The use of the ligand Sphos with Pd(OAc)2 is crucial for the successful implementation of the present cascade process. This synthetic protocol is also applied for the gram-scale synthesis of a trispheridine alkaloid.
- Borah, Ashwini,Gogoi, Pranjal
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supporting information
p. 2200 - 2206
(2016/05/09)
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- Rh2(II)-catalyzed ester migration to afford 3 H-indoles from trisubstituted styryl azides
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Rh2(II)-Complexes trigger the formation of 3H-indoles from ortho-alkenyl substituted aryl azides. This reaction occurs through a 4π-electron-5-atom electrocyclization of the rhodium N-aryl nitrene followed by a [1,2]-migration to afford only 3H-indoles. The selectivity of the migration is dependent on the identity of the β-styryl substituent.
- Kong, Chen,Driver, Tom G.
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supporting information
p. 802 - 805
(2015/04/27)
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- MK2 INHIBITORS AND USES THEREOF
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The present invention provides compounds, compositions thereof, and methods of using the same.
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- Efficient synthesis of 3 H-indoles enabled by the lead-mediated α-arylation of β-ketoesters or γ-lactams using aryl azides
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The development of a lead-mediated α-arylation reaction between aryl azides and β-ketoesters or γ-lactams that facilitates the formation of 3H-indoles is disclosed. Twenty-five examples are included which demonstrate the generality of this reaction to access aryl azides bearing tetrasubstituted o-alkyl substituents. When paired with a Staudinger reduction, this reaction streamlines the synthesis of functionalized 3H-indoles.
- Zhou, Fei,Driver, Tom G.
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supporting information
p. 2916 - 2919
(2014/06/23)
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- Development of a Suzuki cross-coupling reaction between 2-azidoarylboronic pinacolate esters and vinyl triflates to enable the synthesis of [2,3]-fused indole heterocycles
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The scope and limitations of a Suzuki reaction between 2-azidoarylboronic acid pinacolate esters and vinyl triflates are reported. This cross-coupling reaction enables the regioselective synthesis of indoles after a subsequent RhII2-catalyzed sp2-C-H bond amination reaction.
- Jana, Navendu,Nguyen, Quyen,Driver, Tom G.
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p. 2781 - 2791
(2014/04/17)
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- RhII2-catalyzed synthesis of α-, β-, or δ-carbolines from aryl azides
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Approaching all isomers: A range of α-, β- and δ-carbolinium ions are readily available from ortho-substituted aryl azides using a rhodium(II) carboxylate catalyst (see scheme). The carbolinium ions are readily reduced to afford tryptolines or deprotonated to access pyridoindoles. This [RhII2]-catalyzed C-H bond amination was used in the synthesis of (±)-horsfiline and neocryptolepine. esp=α,α,α',α'- tetramethyl-1,3-benzenedipropionate. Copyright
- Pumphrey, Ashley L.,Dong, Huijun,Driver, Tom G.
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supporting information; experimental part
p. 5920 - 5923
(2012/08/07)
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