A Global and Local Desymmetrization Approach to the Synthesis of Steroidal Alkaloids: Stereocontrolled Total Synthesis of Paspaline

Sharpe, Robert J.; Johnson, Jeffrey S.

doi:10.1021/jacs.5b02631

Cited by 84 publications

(42 citation statements)

References 78 publications

(43 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Subsequentl ithium tri-tert-butoxyaluminium hydride mediated reduction and Barton-McCombie deoxygenation [26] of the corresponding alcohol gave ketone 20. [27] Havingp repared 20,wef ound the p-methoxybenzyl ether protecting group to be unstable after the subsequent epoxidation reactiono ft he C9/C10 double bond due to competing intramolecular epoxide opening. Therefore, 20 was converted into silyl ether 21,w hich was then subjected to vinyl triflate formation and subsequent regioselective epoxidation, affording epoxide 22 as am ixture (1:1) of diastereomers.…”

Section: Paternò-büchi Approachmentioning

confidence: 99%

A Divergent Approach to the Marine Diterpenoids (+)‐Dictyoxetane and (+)‐Dolabellane V

Hugelshofer

Magauer

2016

Chemistry A European J

View full text Add to dashboard Cite

We present a full account of the development of a strategy that culminated in the first total syntheses of the unique oxetane-containing natural product (+)-dictyoxetane and the macrocyclic diterpene (+)-dolabellane V. Our retrosynthetic planning was guided by both classical and nonconventional strategies to construct the oxetane, which is embedded in an unprecedented 2,7-dioxatricyclo[4.2.1.0 ]nonane ring system. Highlights of the successful approach include highly diastereoselective carbonyl addition reactions to assemble the full carbon skeleton, a Grob fragmentation to construct the 11-membered macrocycle of (+)-dolabellane V, and a bioinspired 4-exo-tet, 5-exo-trig cyclization sequence to form the complex dioxatricyclic framework of (+)-dictyoxetane. Furthermore, an unprecedented strain-releasing type I dyotropic rearrangement of an epoxide-oxetane substrate was developed.

show abstract

Section: Paternò-büchi Approachmentioning

confidence: 99%

A Divergent Approach to the Marine Diterpenoids (+)‐Dictyoxetane and (+)‐Dolabellane V

Hugelshofer

Magauer

2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Our work toward this goal culminated in a highly stereocontrolled total synthesis of paspaline. 16 Herein, we disclose the entirety of our efforts, ultimately leading to the conception and implementation of two critical stereoselective desymmetrization reactions for facile target assembly. These studies have laid the groundwork for future investigations in this family of natural products.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline

Sharpe

Johnson

2015

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

An enantioselective synthesis of the indole diterpenoid natural product paspaline is disclosed. Critical to this approach was the implementation of stereoselective desymmetrization reactions to assemble key stereocenters of the molecule. The design and execution of these tactics are described in detail, and a thorough analysis of observed outcomes is presented, ultimately providing the title compound in high stereopurity. This synthesis provides a novel template for preparing key stereocenters in this family of molecules, and the reactions developed en route to paspaline present a series of new synthetic disconnections in preparing steroidal natural products.

show abstract

“…Sharpe and Johnson utilized this RCM reactionf or the construction of the Cring of the natural product paspaline. [139]…”

Section: Modification Of Steroidsmentioning

confidence: 99%

“…Subsequent intramolecular Heck reaction under Tietze reaction conditions furnished the B ring of estrone ( 235 ) in quantitative yield. Sharpe and Johnson utilized this RCM reaction for the construction of the C ring of the natural product paspaline …”

Section: Modification Of Steroidsmentioning

confidence: 99%

Homogeneous Catalysis: A Powerful Technology for the Modification of Important Biomolecules

Shelke

Yashmeen

Gholap

et al. 2018

Chemistry An Asian Journal

View full text Add to dashboard Cite

Homogeneous catalysis plays an important and ubiquitous role in the synthesis of simple and complex molecules, including drug compounds, natural products, and agrochemicals. In recent years, the wide-reaching importance of homogeneous catalysis has made it an indispensable tool for the modification of biomolecules, such as carbohydrates (sugars), amino acids, peptides, nucleosides, nucleotides, and steroids. Such a synthetic strategy offers several advantages, which have led to the development of new molecules of biological relevance at a rapid rate relative to the number of available synthetic methods. Given the powerful nature of homogeneous catalysis in effecting these synthetic transformations, this Focus Review has been compiled to highlight these important developments.

show abstract

A Global and Local Desymmetrization Approach to the Synthesis of Steroidal Alkaloids: Stereocontrolled Total Synthesis of Paspaline

Cited by 84 publications

References 78 publications

A Divergent Approach to the Marine Diterpenoids (+)‐Dictyoxetane and (+)‐Dolabellane V

A Divergent Approach to the Marine Diterpenoids (+)‐Dictyoxetane and (+)‐Dolabellane V

Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline

Homogeneous Catalysis: A Powerful Technology for the Modification of Important Biomolecules

Contact Info

Product

Resources

About