The Experts below are selected from a list of 243 Experts worldwide ranked by ideXlab platform
Javier Read De Alaniz - One of the best experts on this subject based on the ideXlab platform.
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Enantioselective PCCP Brønsted acid-catalyzed aza-Piancatelli Rearrangement.
Beilstein journal of organic chemistry, 2019Co-Authors: Gabrielle Hammersley, Gesine K Veits, Meghan F. Nichol, Helena C Steffens, Jose M Delgado, Javier Read De AlanizAbstract:An enantioselective aza-Piancatelli Rearrangement has been developed using a chiral Bronsted acid based on pentacarboxycyclopentadiene (PCCP). This reaction provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available starting material and is operationally simple.
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cascade Rearrangement of furylcarbinols with hydroxylamines practical access to densely functionalized cyclopentane derivatives
Organic and Biomolecular Chemistry, 2015Co-Authors: Gesine K Veits, Donald R Wenz, Leoni I Palmer, Andre H St Amant, Jason E Hein, Javier Read De AlanizAbstract:This article describes the aza-Piancatelli Rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation.
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Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
ACS Catalysis, 2015Co-Authors: Ryan Chung, Gesine K Veits, Javier Read De Alaniz, Van T. Thai, Alyssa F. Jones, Jason E HeinAbstract:Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variables—such as temperature, time, concentration, etc.—to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli Rearrangement of 2-furylcarbinols, a reaction that...
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Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
2015Co-Authors: Van T. Thai, Gesine K Veits, Javier Read De Alaniz, Jonathan E. Cook, Leoni I. Palmer, Jason E HeinAbstract:The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli Rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Brønsted or Lewis acid catalyst and that the resulting Rearrangement proceeds without involving the Brønsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled
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Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
2015Co-Authors: Ryan Chung, Gesine K Veits, Javier Read De Alaniz, Van T. Thai, Alyssa F. Jones, Jason E HeinAbstract:Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variablessuch as temperature, time, concentration, etc.to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli Rearrangement of 2-furylcarbinols, a reaction that grants access to trans-4,5-disubstituted cyclopentenonescommon motifs in important biologically relevant and natural compounds. With a prototype automated sampling apparatus, information was obtained about the intrinsic chemoselectivity of the reaction, and previously unseen intermediates were observed, allowing for a more detailed reaction mechanism to be substantiated. The advantages of applying this type of tandem measurement to study these types of systems are also discussed
Srivari Chandrasekhar - One of the best experts on this subject based on the ideXlab platform.
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Cation Triggered Domino Aza-Piancatelli Rearrangement/Friedel–Crafts Alkylation of Indole-Tethered Furfuyl Alcohols to Access Cycloocta[b]indole Core of Alkaloids
Organic letters, 2020Co-Authors: Nagarjuna Reddy Vonteddu, Pooja R. Solanke, Kiranmai Nayani, Srivari ChandrasekharAbstract:A domino approach to bridged cycloocta[b]indolone through a cascade of aza-Piancatelli Rearrangement/Friedel-Crafts alkylation is developed. This transformation has been realized by reaction of an indole-tethered 2-furylcarbinol and substituted aniline in the presence of a Lewis acid to initiate aza-Piancatelli Rearrangement followed by an in situ intramolecular Friedel-Crafts alkylation to access bridged tetracyclic frameworks in one pot.
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cation triggered domino aza Piancatelli Rearrangement friedel crafts alkylation of indole tethered furfuyl alcohols to access cycloocta b indole core of alkaloids
Organic Letters, 2020Co-Authors: Nagarjuna Reddy Vonteddu, Pooja R. Solanke, Kiranmai Nayani, Srivari ChandrasekharAbstract:A domino approach to bridged cycloocta[b]indolone through a cascade of aza-Piancatelli Rearrangement/Friedel-Crafts alkylation is developed. This transformation has been realized by reaction of an indole-tethered 2-furylcarbinol and substituted aniline in the presence of a Lewis acid to initiate aza-Piancatelli Rearrangement followed by an in situ intramolecular Friedel-Crafts alkylation to access bridged tetracyclic frameworks in one pot.
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Brønsted Acid Catalyzed Domino Aza‐Piancatelli Rearrangement/Michael Reaction: Construction of 1,4‐Benzodiazepin‐5‐ones in One Pot
European Journal of Organic Chemistry, 2017Co-Authors: Kiranmai Nayani, Radhika Cinsani, Prathama S. Mainkar, Srivari ChandrasekharAbstract:A pTSA catalyzed domino aza-Piancatelli Rearrangement/Michael reaction was developed for the construction of 1,4-benzodiazepin-5-ones in one pot. The methodological studies offer broad scope and proceed well with various furfuryl carbinols as well as o-aminobenzamides giving medicinally relevant new chemical entities.
Biaolin Yin - One of the best experts on this subject based on the ideXlab platform.
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Synthesis, Skeletal Rearrangement, and Biological Activities of Spirooxindoles: Exploration of a Stepwise C-Piancatelli Rearrangement.
ChemInform, 2014Co-Authors: Li Huang, Xiaoyu Zhang, Ke Ding, Wenxu Zheng, Biaolin YinAbstract:The transformation of 2-furylcarbinols into spirofurooxindoles and their subsequent thermal skeletal Rearrangement are studied.
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synthesis skeletal Rearrangement and biological activities of spirooxindoles exploration of a stepwise c Piancatelli Rearrangement
European Journal of Organic Chemistry, 2014Co-Authors: Li Huang, Xiaoyu Zhang, Ke Ding, Wenxu Zheng, Biaolin YinAbstract:Based on our previous studies, the scope of the transformation of 2-furylcarbinols into spirofurooxindoles, and also the skeletal Rearrangements of spiro[furo-oxindoles] and spiro[thieno-oxindoles] were studied. The spiro[furo-oxindoles] thermally rearranged into spiro[pentenone-oxindoles] by a mechanism involving the conrotatory electrocyclization of the 4π-electron system. The free energy of the electrocyclization step was calculated to interpret the stereochemical outcomes. In contrast, the spiro[thieno-oxindoles] were rearranged under acidic conditions into thieno[2,3-c]quinolin-4-ones, involving an interesting dienone–phenol-like mechanism. The transformation of 2-furylcarbinols into spiro[pentenone-oxindoles] seems to be the first stepwise C-Piancatelli Rearrangement. The spirooxindole products were biologically evaluated, and some of them showed promising cytotoxic activities against DU145 and LNCaP tumor cell lines.
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Synthesis, Skeletal Rearrangement, and Biological Activities of Spirooxindoles: Exploration of a Stepwise C‐Piancatelli Rearrangement
European Journal of Organic Chemistry, 2013Co-Authors: Li Huang, Xiaoyu Zhang, Ke Ding, Wenxu Zheng, Biaolin YinAbstract:Based on our previous studies, the scope of the transformation of 2-furylcarbinols into spirofurooxindoles, and also the skeletal Rearrangements of spiro[furo-oxindoles] and spiro[thieno-oxindoles] were studied. The spiro[furo-oxindoles] thermally rearranged into spiro[pentenone-oxindoles] by a mechanism involving the conrotatory electrocyclization of the 4π-electron system. The free energy of the electrocyclization step was calculated to interpret the stereochemical outcomes. In contrast, the spiro[thieno-oxindoles] were rearranged under acidic conditions into thieno[2,3-c]quinolin-4-ones, involving an interesting dienone–phenol-like mechanism. The transformation of 2-furylcarbinols into spiro[pentenone-oxindoles] seems to be the first stepwise C-Piancatelli Rearrangement. The spirooxindole products were biologically evaluated, and some of them showed promising cytotoxic activities against DU145 and LNCaP tumor cell lines.
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Metal-Free Rearrangement of Spirofurooxindoles into Spiropentenoneoxindoles and Indoles: Implications for the Mechanism and Stereochemistry of the Piancatelli Rearrangement.
ChemInform, 2013Co-Authors: Biaolin Yin, Li Huang, Xiujun Wang, Jianchao Liu, Huanfeng JiangAbstract:Spirofurooxindoles (I) derived from α-furylcarbinols are rearranged into spirocyclopentenoneoxindole diastereomers (II)/(III) in refluxing DCE.
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metal free Rearrangement of spirofurooxindoles into spiropentenoneoxindoles and indoles implications for the mechanism and stereochemistry of the Piancatelli Rearrangement
Advanced Synthesis & Catalysis, 2013Co-Authors: Biaolin Yin, Li Huang, Xiujun Wang, Jianchao Liu, Huanfeng JiangAbstract:Spirofurooxindoles derived from α-furylcarbinols were rearranged into spirocyclopentenoneoxindoles exclusively or as a mixture of spirocyclopentenoneoxindoles and indoles under different reaction conditions. Along with our previous studies, the stepwise C-Piancatelli Rearrangement has been presented for the first time.
Kiranmai Nayani - One of the best experts on this subject based on the ideXlab platform.
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Cation Triggered Domino Aza-Piancatelli Rearrangement/Friedel–Crafts Alkylation of Indole-Tethered Furfuyl Alcohols to Access Cycloocta[b]indole Core of Alkaloids
Organic letters, 2020Co-Authors: Nagarjuna Reddy Vonteddu, Pooja R. Solanke, Kiranmai Nayani, Srivari ChandrasekharAbstract:A domino approach to bridged cycloocta[b]indolone through a cascade of aza-Piancatelli Rearrangement/Friedel-Crafts alkylation is developed. This transformation has been realized by reaction of an indole-tethered 2-furylcarbinol and substituted aniline in the presence of a Lewis acid to initiate aza-Piancatelli Rearrangement followed by an in situ intramolecular Friedel-Crafts alkylation to access bridged tetracyclic frameworks in one pot.
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cation triggered domino aza Piancatelli Rearrangement friedel crafts alkylation of indole tethered furfuyl alcohols to access cycloocta b indole core of alkaloids
Organic Letters, 2020Co-Authors: Nagarjuna Reddy Vonteddu, Pooja R. Solanke, Kiranmai Nayani, Srivari ChandrasekharAbstract:A domino approach to bridged cycloocta[b]indolone through a cascade of aza-Piancatelli Rearrangement/Friedel-Crafts alkylation is developed. This transformation has been realized by reaction of an indole-tethered 2-furylcarbinol and substituted aniline in the presence of a Lewis acid to initiate aza-Piancatelli Rearrangement followed by an in situ intramolecular Friedel-Crafts alkylation to access bridged tetracyclic frameworks in one pot.
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bronsted acid catalyzed domino aza Piancatelli Rearrangement michael reaction construction of 1 4 benzodiazepin 5 ones in one pot
European Journal of Organic Chemistry, 2017Co-Authors: Kiranmai Nayani, Radhika Cinsani, Prathama S. Mainkar, S ChandrasekharAbstract:A pTSA catalyzed domino aza-Piancatelli Rearrangement/Michael reaction was developed for the construction of 1,4-benzodiazepin-5-ones in one pot. The methodological studies offer broad scope and proceed well with various furfuryl carbinols as well as o-aminobenzamides giving medicinally relevant new chemical entities.
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Brønsted Acid Catalyzed Domino Aza‐Piancatelli Rearrangement/Michael Reaction: Construction of 1,4‐Benzodiazepin‐5‐ones in One Pot
European Journal of Organic Chemistry, 2017Co-Authors: Kiranmai Nayani, Radhika Cinsani, Prathama S. Mainkar, Srivari ChandrasekharAbstract:A pTSA catalyzed domino aza-Piancatelli Rearrangement/Michael reaction was developed for the construction of 1,4-benzodiazepin-5-ones in one pot. The methodological studies offer broad scope and proceed well with various furfuryl carbinols as well as o-aminobenzamides giving medicinally relevant new chemical entities.
Jason E Hein - One of the best experts on this subject based on the ideXlab platform.
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cascade Rearrangement of furylcarbinols with hydroxylamines practical access to densely functionalized cyclopentane derivatives
Organic and Biomolecular Chemistry, 2015Co-Authors: Gesine K Veits, Donald R Wenz, Leoni I Palmer, Andre H St Amant, Jason E Hein, Javier Read De AlanizAbstract:This article describes the aza-Piancatelli Rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation.
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Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
ACS Catalysis, 2015Co-Authors: Ryan Chung, Gesine K Veits, Javier Read De Alaniz, Van T. Thai, Alyssa F. Jones, Jason E HeinAbstract:Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variables—such as temperature, time, concentration, etc.—to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli Rearrangement of 2-furylcarbinols, a reaction that...
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Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
2015Co-Authors: Van T. Thai, Gesine K Veits, Javier Read De Alaniz, Jonathan E. Cook, Leoni I. Palmer, Jason E HeinAbstract:The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli Rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Brønsted or Lewis acid catalyst and that the resulting Rearrangement proceeds without involving the Brønsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled
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Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
2015Co-Authors: Ryan Chung, Gesine K Veits, Javier Read De Alaniz, Van T. Thai, Alyssa F. Jones, Jason E HeinAbstract:Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variablessuch as temperature, time, concentration, etc.to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli Rearrangement of 2-furylcarbinols, a reaction that grants access to trans-4,5-disubstituted cyclopentenonescommon motifs in important biologically relevant and natural compounds. With a prototype automated sampling apparatus, information was obtained about the intrinsic chemoselectivity of the reaction, and previously unseen intermediates were observed, allowing for a more detailed reaction mechanism to be substantiated. The advantages of applying this type of tandem measurement to study these types of systems are also discussed
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Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
The Journal of organic chemistry, 2013Co-Authors: Van T. Thai, Gesine K Veits, Leoni I Palmer, Javier Read De Alaniz, Jonathan E. Cook, Jason E HeinAbstract:The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli Rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Bronsted or Lewis acid catalyst and that the resulting Rearrangement proceeds without involving the Bronsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled.
