Total Synthesis Of 1,10-Diphenylbicyclo[8.8.8]hexacos-5-ene

A multi-gram, flexible, customizable, scalable total synthesis of 1,10-diphenylbicyclo[8.8.8]hexacos-5-ene over 15 steps has been developed. The synthesis was engineered pushing most difunctional intermediates to quantitative completion thereby mini-mizing purification steps. The multi-gram synthesis can be conveniently performed by a single worker. Only four major purification steps are required, one involving the separation of dia-stereomers on 50-gram scale, and two chromatographic separations late in the synthesis on a conventionally manageable scale. The features of the work include a rare example of a large-scale RCM macrocyclization method useful on industrial scales, and the development of a multi-gram chromatographic method that allows reasonable separations using minimal amounts of silica (close to dry-loading amounts) and solvent. LAH workup was developed that is fast and safe, not requiring liquid-liquid extraction or the use of solvent drying agents. In-stead, the reaction mixture is simply quenched, filtered, and evaporated under reduced pres-sure. Another notable feature is the use of DCM as the hydrogenation solvent using the palla-dium on carbon catalyst.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Graduate College

Grantor dc:publisher

The University of Arizona.

Year dc:date.issued

2023

Author dc:creator

• Timofeyenko, Yegor Georgievich

Advisor dc:contributor.advisor

• Mash, Jr, Eugene A.

Committee members dc:contributor.committeemember

• Jewett, John
• Loy, Douglas A.
• Christie, Hamish

Statement dc:rights

• Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction, presentation (such as public display or performance) of protected items is prohibited except with permission of the author.

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Handle dc:identifier.uri

http://hdl.handle.net/10150/670849

OAI identifier oai:identifier

oai:repository.arizona.edu:10150/670849