Author: Phillip Conrad Knutson
Publisher:
ISBN:
Category :
Languages : en
Pages : 1108
Book Description
The Gelsemium alkaloids represent a diverse class of natural products that have displayed interesting biological and medicinal properties. Because of their pharmacological interest as well as inherent synthetic challenges, chemists have been tackling the construction of these molecules for decades. Many of the Gelsemium alkaloids share a characteristic oxabicyclic core that is both densely packed and relatively unfunctionalized. We noticed that this core could be generated rapidly through a tandem cycloisomerization/Cope rearrangement. Through our execution of this methodology we were able to accomplish the total syntheses of Gelsenicine and Gelsedine. These total syntheses represent an entry into a divergent total synthesis program. Through the synthesis of a common core through the tandem cycloisomerization/Cope rearrangement, we envision access to other members of the Gelsemium alkaloid family, such as Gelsemoxonine. We have also demonstrated the enantioselective total synthesis of Gelsenicine through an enantioselective gold-catalyzed cycloisomerization. This was accomplished by using chiral ligands such as phosphoramidites and bisphosphines. We found that bisphosphine ligands bearing electron rich and bulky aryl substituents on phosphorous worked well to give high levels of asymmetric induction in the cycloisomerization product. Lastly, a convenient Cadiot8́2Chodkiewicz protocol that facilitates the use of low molecular weight alkyne coupling partners is described. The method entails an in situ elimination from a dibromooleƠ̐1n precursor and immediate subjection to copper-catalyzed conditions, circumventing the hazards of volatile brominated alkynes. The scope of this method is described, and the internal 1,3-diyne products are preliminarily evaluated in ruthenium-catalyzed azide-alkyne cycloadditions.
Studies in the Total Synthesis of the Gelsemium Alkaloids
Author: Phillip Conrad Knutson
Publisher:
ISBN:
Category :
Languages : en
Pages : 1108
Book Description
The Gelsemium alkaloids represent a diverse class of natural products that have displayed interesting biological and medicinal properties. Because of their pharmacological interest as well as inherent synthetic challenges, chemists have been tackling the construction of these molecules for decades. Many of the Gelsemium alkaloids share a characteristic oxabicyclic core that is both densely packed and relatively unfunctionalized. We noticed that this core could be generated rapidly through a tandem cycloisomerization/Cope rearrangement. Through our execution of this methodology we were able to accomplish the total syntheses of Gelsenicine and Gelsedine. These total syntheses represent an entry into a divergent total synthesis program. Through the synthesis of a common core through the tandem cycloisomerization/Cope rearrangement, we envision access to other members of the Gelsemium alkaloid family, such as Gelsemoxonine. We have also demonstrated the enantioselective total synthesis of Gelsenicine through an enantioselective gold-catalyzed cycloisomerization. This was accomplished by using chiral ligands such as phosphoramidites and bisphosphines. We found that bisphosphine ligands bearing electron rich and bulky aryl substituents on phosphorous worked well to give high levels of asymmetric induction in the cycloisomerization product. Lastly, a convenient Cadiot8́2Chodkiewicz protocol that facilitates the use of low molecular weight alkyne coupling partners is described. The method entails an in situ elimination from a dibromooleƠ̐1n precursor and immediate subjection to copper-catalyzed conditions, circumventing the hazards of volatile brominated alkynes. The scope of this method is described, and the internal 1,3-diyne products are preliminarily evaluated in ruthenium-catalyzed azide-alkyne cycloadditions.
Publisher:
ISBN:
Category :
Languages : en
Pages : 1108
Book Description
The Gelsemium alkaloids represent a diverse class of natural products that have displayed interesting biological and medicinal properties. Because of their pharmacological interest as well as inherent synthetic challenges, chemists have been tackling the construction of these molecules for decades. Many of the Gelsemium alkaloids share a characteristic oxabicyclic core that is both densely packed and relatively unfunctionalized. We noticed that this core could be generated rapidly through a tandem cycloisomerization/Cope rearrangement. Through our execution of this methodology we were able to accomplish the total syntheses of Gelsenicine and Gelsedine. These total syntheses represent an entry into a divergent total synthesis program. Through the synthesis of a common core through the tandem cycloisomerization/Cope rearrangement, we envision access to other members of the Gelsemium alkaloid family, such as Gelsemoxonine. We have also demonstrated the enantioselective total synthesis of Gelsenicine through an enantioselective gold-catalyzed cycloisomerization. This was accomplished by using chiral ligands such as phosphoramidites and bisphosphines. We found that bisphosphine ligands bearing electron rich and bulky aryl substituents on phosphorous worked well to give high levels of asymmetric induction in the cycloisomerization product. Lastly, a convenient Cadiot8́2Chodkiewicz protocol that facilitates the use of low molecular weight alkyne coupling partners is described. The method entails an in situ elimination from a dibromooleƠ̐1n precursor and immediate subjection to copper-catalyzed conditions, circumventing the hazards of volatile brominated alkynes. The scope of this method is described, and the internal 1,3-diyne products are preliminarily evaluated in ruthenium-catalyzed azide-alkyne cycloadditions.
Gelsemium Alkaloids
Author: Daniel Kuzmich
Publisher:
ISBN:
Category :
Languages : en
Pages : 850
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 850
Book Description
Approaches to the Total Synthesis of the Alkaloids of Gelsemium Species
Author: Keith Mills
Publisher:
ISBN:
Category :
Languages : en
Pages :
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages :
Book Description
Progress Toward the First Total Synthesis of ( - )-Gelsemicine
Author: Christopher Roy Goss
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 256
Book Description
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 256
Book Description
A Study of the Preparation and Use of Chiral Cyclic C-acyl Nitrones ; Studies Directed Toward the Total Synthesis of Gelsemicine
Author: Paul Greenspan
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 366
Book Description
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 366
Book Description
Studies Toward the Synthesis of Gelsemicine
Author: M. T. Diaz
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 130
Book Description
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 130
Book Description
Studies Directed Toward the Total Syntheses of the Gelsemium Alkaloids ...
Author: Ronald James Doll
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 254
Book Description
Publisher:
ISBN:
Category : Alkaloids
Languages : en
Pages : 254
Book Description
Studies Toward the Toward the Total Synthesis of the Alkaloids Gelsedine and Manzamine A
Author: Scott A. Ballentine
Publisher:
ISBN:
Category :
Languages : en
Pages : 514
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 514
Book Description
Studies Towards a Total Synthesis of the Oxindole Alkaloid Gelsemine
Author: Ya (Fang.)
Publisher:
ISBN:
Category :
Languages : en
Pages : 115
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 115
Book Description
Studies Towards Total Synthesis of Polyketide Natural Products and Alkaloids
Author: Anastasia Hager
Publisher:
ISBN:
Category :
Languages : de
Pages :
Book Description
Publisher:
ISBN:
Category :
Languages : de
Pages :
Book Description