scholarly journals Synthesis of (−)-Picrotoxinin by Late-Stage Strong Bond Activation

2020 ◽  
Vol 142 (26) ◽  
pp. 11376-11381 ◽  
Author(s):  
Steven W. M. Crossley ◽  
Guanghu Tong ◽  
Michael J. Lambrecht ◽  
Hannah E. Burdge ◽  
Ryan A. Shenvi
Keyword(s):  
Late Stage ◽  
Bond Activation ◽  
Strong Bond ◽  
Strong Bond Activation

Late-Stage Carbon Isotope Exchange of Aryl Nitriles through Ni-Catalyzed C–CN Bond Activation

2021 ◽  
Vol 143 (12) ◽  
pp. 4817-4823
Author(s):  
Sean W. Reilly ◽  
Yu-hong Lam ◽  
Sumei Ren ◽  
Neil A. Strotman
Keyword(s):  
Carbon Isotope ◽  
Late Stage ◽  
Isotope Exchange ◽  
Bond Activation ◽  
Aryl Nitriles

scholarly journals Nickel-Catalyzed Thiolation of Aryl Nitriles

2021 ◽  
Author(s):  
Tristan Delcaillau ◽  
Bill Morandi
Keyword(s):  
Late Stage ◽  
Functional Group ◽  
Bond Activation ◽  
Bond Formation ◽  
Aryl Nitriles

<div>A nickel-catalyzed thiolation of aryl nitriles has been developed to access functionalized aryl thioethers. The ligand dcype (1,2 Bis(dicyclohexylphosphino)ethane) as well as the base KOtBu (potassium tert-butoxide) are essential to achieve this transformation. This scalable and practical process involves both a C–C bond activation and a C–S bond formation. Furthermore, this reaction shows a high functional-group tolerance and enables the late-stage functionalization of important molecules.</div>

Late-Stage Carbon Isotope Exchange of Aryl Nitriles through Ni-Catalyzed C–CN Bond Activation

2021 ◽  
Author(s):  
Sean Reilly ◽  
Yu-hong Lam ◽  
Sumei Ren ◽  
Neil Strotman
Keyword(s):  
Carbon Isotope ◽  
Late Stage ◽  
Isotope Exchange ◽  
Functional Group ◽  
Bond Activation ◽  
De Novo ◽  
Parent Compound ◽  
One Pot ◽  
Aryl Nitriles ◽  
Labeling Approach

<div> <p>A facile one-pot strategy for <sup>13</sup>CN and <sup>14</sup>CN exchange with aryl, heteroaryl, and vinyl nitriles using a Ni phosphine catalyst and BPh<sub>3</sub> is described. This late-stage carbon isotope exchange (CIE) strategy employs labeled Zn(CN)<sub>2</sub> to facilitate enrichment using the non-labeled parent compound as the starting material, eliminating <i>de novo</i> synthesis for precursor development. A broad substrate scope encompassing multiple pharmaceuticals is disclosed, including the preparation of [<sup>14</sup>C]<a>belzutifan</a> to illustrate the exceptional functional group tolerance and utility of this labeling approach. Preliminary experimental and computational studies suggest the Lewis acid BPh<sub>3</sub> is not critical for the oxidative addition step and instead plays a role in facilitating CN exchange on Ni. This CIE method dramatically reduces the synthetic steps and radioactive waste involved in preparation of <sup>14</sup>C labeled tracers for clinical development.</p> </div>

ChemInform Abstract: Pd-Catalyzed Late-Stage Monoacetoxylation and Monoiodination of 4-Alkyl-1,5-diaryl-1H-pyrazole-3-carboxylates via Direct Csp2-H Bond Activation.

ChemInform ◽  
2016 ◽  
Vol 47 (36) ◽  
Author(s):  
Xue-Min Fan ◽  
Ying Guo ◽  
Yu-Dan Li ◽  
Kun-Kun Yu ◽  
Hong-Wei Liu ◽  
...  
Keyword(s):  
Late Stage ◽  
Bond Activation

Pd‐Catalyzed Late‐Stage Monoacetoxylation and Monoiodination of 4‐Alkyl‐1,5‐diaryl‐1  H ‐pyrazole‐3‐carboxylates via Direct Csp 2 −H Bond Activation

2016 ◽  
Vol 5 (4) ◽  
pp. 499-505 ◽  
Author(s):  
Xue‐Min Fan ◽  
Ying Guo ◽  
Yu‐Dan Li ◽  
Kun‐Kun Yu ◽  
Hong‐Wei Liu ◽  
...  
Keyword(s):  
Late Stage ◽  
Bond Activation

scholarly journals The Enones as New Alkenyl Reagents via Ligand Promoted C–C Bonds Activation

2021 ◽  
Author(s):  
Hanyuan Li ◽  
Mei-Ling Wang ◽  
Yue-Wen Liu ◽  
Ling-Jun Li ◽  
Hui Xu ◽  
...  
Keyword(s):  
Natural Products ◽  
Late Stage ◽  
Functional Group ◽  
Bond Activation ◽  
Potential Utility ◽  
One Pot ◽  
Complex Molecules ◽  
The Past

Complementary to C–H bond activation, C–C bond activation has emerged over the past few years as an increasingly powerful tool to access and modify complex molecules. Ketones, owing to their versatility and availability, provide a significant platform for C–C bond activating reactions. Herein, we reported a <i>β</i>-carbon elimination strategy for alkene(sp<sup>2</sup>)–C(O) bonds to realize the olefination of unstrained enones via a vinyl palladium species, which delivers a series of conjugated polyene compounds. The protocol features broad substrate scope, excellent functional group tolerance and can be extended to dba (dibenzylideneacetone) substrates for olefination, alkynylation, arylation and amination, which demonstrates the generality of the approach and affords two valuable products in one pot. Furthermore, the late-stage functionalization of natural products (<i>β</i>-ionone and acetyl cedrene) and synthesis of natural products (piperine, lignarenone, novenone) highlight the potential utility of the reaction.

scholarly journals Late-Stage Carbon Isotope Exchange of Aryl Nitriles through Ni-Catalyzed C–CN Bond Activation

2021 ◽  
Author(s):  
Sean Reilly ◽  
Yu-hong Lam ◽  
Sumei Ren ◽  
Neil Strotman
Keyword(s):  
Carbon Isotope ◽  
Late Stage ◽  
Isotope Exchange ◽  
Functional Group ◽  
Bond Activation ◽  
De Novo ◽  
Parent Compound ◽  
One Pot ◽  
Aryl Nitriles ◽  
Labeling Approach

<div> <p>A facile one-pot strategy for <sup>13</sup>CN and <sup>14</sup>CN exchange with aryl, heteroaryl, and vinyl nitriles using a Ni phosphine catalyst and BPh<sub>3</sub> is described. This late-stage carbon isotope exchange (CIE) strategy employs labeled Zn(CN)<sub>2</sub> to facilitate enrichment using the non-labeled parent compound as the starting material, eliminating <i>de novo</i> synthesis for precursor development. A broad substrate scope encompassing multiple pharmaceuticals is disclosed, including the preparation of [<sup>14</sup>C]<a>belzutifan</a> to illustrate the exceptional functional group tolerance and utility of this labeling approach. Preliminary experimental and computational studies suggest the Lewis acid BPh<sub>3</sub> is not critical for the oxidative addition step and instead plays a role in facilitating CN exchange on Ni. This CIE method dramatically reduces the synthetic steps and radioactive waste involved in preparation of <sup>14</sup>C labeled tracers for clinical development.</p> </div>

scholarly journals The Enones as New Alkenyl Reagents via Ligand Promoted C–C Bonds Activation

2021 ◽  
Author(s):  
Hanyuan Li ◽  
Mei-Ling Wang ◽  
Yue-Wen Liu ◽  
Ling-Jun Li ◽  
Hui Xu ◽  
...  
Keyword(s):  
Natural Products ◽  
Late Stage ◽  
Functional Group ◽  
Bond Activation ◽  
Potential Utility ◽  
One Pot ◽  
Complex Molecules ◽  
The Past

Complementary to C–H bond activation, C–C bond activation has emerged over the past few years as an increasingly powerful tool to access and modify complex molecules. Ketones, owing to their versatility and availability, provide a significant platform for C–C bond activating reactions. Herein, we reported a <i>β</i>-carbon elimination strategy for alkene(sp<sup>2</sup>)–C(O) bonds to realize the olefination of unstrained enones via a vinyl palladium species, which delivers a series of conjugated polyene compounds. The protocol features broad substrate scope, excellent functional group tolerance and can be extended to dba (dibenzylideneacetone) substrates for olefination, alkynylation, arylation and amination, which demonstrates the generality of the approach and affords two valuable products in one pot. Furthermore, the late-stage functionalization of natural products (<i>β</i>-ionone and acetyl cedrene) and synthesis of natural products (piperine, lignarenone, novenone) highlight the potential utility of the reaction.

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