Expedient one-step synthesis of nitrogen stilbene analogs by transition metal-free hydroamination of arylacetylenes with pyrroles

Dvorko, Marina Yu.; Schmidt, Elena Yu.; Glotova, T. E.; Shabalin, Dmitrii A.; Ushakov, Igor А.; Кобычев, В. Б.; Petrushenko, Konstantin B.; Михалева, А. И.; Трофимов, Б. А.

doi:10.1016/j.tet.2011.12.050

Cited by 19 publications

(12 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Surprisingly, the KOH/DMSO‐catalyzed [4+2] cycloaddition of acetylenes to tetrazine 1 here observed entirely suppresses the expected N ‐vinylation of the pyrrole moieties, usually feasible under the same conditions 15…”

Section: Synthesis Of 36‐di(pyrrol‐2‐yl)pyridazines 3 From 1245‐tmentioning

confidence: 80%

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

et al. 2013

Self Cite

View full text Add to dashboard Cite

Acetylenes undergo the [4 + 2] cycloaddition to 3,6-di(pyrrol-2-yl)-1,2,4,5-tetrazine in the potassium hydroxide/dimethyl sulfoxide or potassium tert-butoxide/dimethyl sulfoxide systems (80 8C, 2.5-4 h) to afford (after extrusion of the nitrogen molecule from the intermediate) 3,6-di(pyrrol-2-yl)pyridazines in up to 73% yield, while under non-catalytic conditions this reaction does not take place. This unusual result substantially extends the scope of synthetic application and mechanistic diversity of the Diels-Alder reaction. The step-wise mechanisms involving the formation of [OH/tetrazine] À or [t-BuO/tetrazine] À anionic intermediate complexes or cycloaddition of tetrazine to the acetylide anion are considered.

show abstract

Section: Synthesis Of 36‐di(pyrrol‐2‐yl)pyridazines 3 From 1245‐tmentioning

confidence: 80%

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…The groups of Knochel,– Ackermann,– Zhang, Stradiotto, and our group– have investigated the application of hydroamination chemistry in the synthesis of various N‐heterocycles using transition metals. Recently Trofimov and co‐workers and we– have explored the superbasic system (KOH/DMSO) with an unusual basicity ( p K a =30–32) for nucleophilic additions of N‐heterocycles onto alkynes. However, to the best of our knowledge, regio‐ and stereoselective preferential hydrothiolation of haloaryl alkynes over S‐arylation of aryl halides has not been reported.…”

Section: Methodsmentioning

confidence: 99%

Nucleophilic Addition versus S_NAr Study: Chemo‐, Regio‐ and Stereoselective Hydrothiolation of Haloaryl Alkynes over S‐Arylation of Aryl Halides

et al. 2015

View full text Add to dashboard Cite

show abstract

“…By using 1 H NMR spectroscopy, the E and Z isomers of the synthesized molecules have been identified . However, an analysis of the spatial and electronic structure of the obtained isomers has not yet been carried out.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, a transition metal‐free hydroamination of arylacetylenes with substituted pyrroles in the superbasic system KOH/DMSO providing a general straightforward route to nitrogen analogs of stilbenes, diversely substituted 1‐styrylpyrroles, has been developed . The novel pyrrole analogs of stilbenes thus synthesized represent promising highly potent synthetic intermediates, building blocks for drug design and precursors for optoelectronic advanced materials, particularly for molecular optical switches, biological labels, sensors, ligands for metallocomplexes and information recording/storage devices…”

Section: Introductionmentioning

confidence: 99%

Structural peculiarities of configurational isomers of 1‐styrylpyrroles according to ¹Н, ¹³С and ¹⁵N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure

Afonin

Ushakov²,

Павлов³

et al. 2013

Magnetic Reson in Chemistry

Self Cite

View full text Add to dashboard Cite

Comparative analysis of the (1)Н and (13)С NMR data for a series of the E and Z-1-styrylpyrroles, E and Z-1-(1-propenyl)pyrroles, 1-vinylpyrroles and styrene suggests that the conjugation between the unsaturated fragments in the former compounds is reduced. This is the result of the mutual influence of the donor p-π and π-π conjugation having opposite directions. According to the NMR data combined with the density functional theory calculations, the Z isomer of 1-styrylpyrrole has essentially a nonplanar structure because of the steric hindrance. However, the E isomer of 1-styrylpyrrole is also an out-of-plane structure despite the absence of a sterical barrier for the planar one. Deviation of the E isomer from the planar structure seems to be caused by an electronic hindrance produced by a mutual influence of the p-π and π-π conjugation. The structure of the E isomer of the 2-substituted 1-styrylpyrroles is similar to that of the 2-substituted 1-vinylpyrroles. The steric effects in the Z isomer of the 2-substituted 1-styrylpyrroles result in the large increase of the dihedral angle between planes of the pyrrole ring and double bond.

show abstract

Expedient one-step synthesis of nitrogen stilbene analogs by transition metal-free hydroamination of arylacetylenes with pyrroles

Cited by 19 publications

References 43 publications

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

Nucleophilic Addition versus S_NAr Study: Chemo‐, Regio‐ and Stereoselective Hydrothiolation of Haloaryl Alkynes over S‐Arylation of Aryl Halides

Structural peculiarities of configurational isomers of 1‐styrylpyrroles according to ¹Н, ¹³С and ¹⁵N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure

Contact Info

Product

Resources

About

Expedient one-step synthesis of nitrogen stilbene analogs by transition metal-free hydroamination of arylacetylenes with pyrroles

Cited by 19 publications

References 43 publications

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

Superbase‐Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6‐Di(pyrrol‐2‐yl)‐1,2,4,5‐tetrazine: A Facile Synthesis of 3,6‐Di(pyrrol‐2‐yl)pyridazines

Nucleophilic Addition versus SNAr Study: Chemo‐, Regio‐ and Stereoselective Hydrothiolation of Haloaryl Alkynes over S‐Arylation of Aryl Halides

Structural peculiarities of configurational isomers of 1‐styrylpyrroles according to 1Н, 13С and 15N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure

Contact Info

Product

Resources

About

Nucleophilic Addition versus S_NAr Study: Chemo‐, Regio‐ and Stereoselective Hydrothiolation of Haloaryl Alkynes over S‐Arylation of Aryl Halides

Structural peculiarities of configurational isomers of 1‐styrylpyrroles according to ¹Н, ¹³С and ¹⁵N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure