Graduate Thesis Or Dissertation
 

Photochemistry of 6-alkenyl-2-cyclohexenones : synthetic studies towards precursors of ryanodol

公开 Deposited

可下载的内容

下载PDF文件
https://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/5425kc98x

Descriptions

Attribute NameValues
Creator
Abstract
  • Regiochemistry of intramolecular [2+2] photocycloadditions of oxygenated 6-alkenyl-3-alkoxy-2-cyclohexenones is studied. Application of this methodology to construct a key intermediate [3.3.2] bicyclic skeleton of ryanodol is described as well. Irradiation of (3-butenyl)compounds 3, 11, 14 and of (4-pentenyl)compound 6 afforded exclusively the linear photoadducts 4, 12, 15 and 7 respectively. Irradiation of allyl compound 25 brought the desired crossed photoadduct 26. The structures of the photoadducts 4, 7 and 26 were assigned based on spectroscopic analysis and confirmed by subsequent retroaldol cleavage reactions of the corresponding photoproducts. The regiochemistry of linear adduct 15 was deduced by a sequence of transformations. Retroaldol cleavage of the photoadduct 15, followed by transannular reductive coupling with SmI₂, and hydrolysis of the protecting group provided triol 18. PDC oxidation of 18 gave [4.2.2] bicyclic triketone 20 and a cyclic hemiketal 21. Finally, Swern oxidation of 18 confirmed both isomers of photoproduct 15 are linear adducts. Selective retroaldol ring opening of compound 26 resulted in the formation of the bicyclo[3.3.1]nonane skeleton, amenable through a one carbon ring expansion to establish the core bicyclo[3.3.2]decane system in ryanodol.
Resource Type
Date Available
Date Issued
Degree Level
Degree Name
Degree Field
Degree Grantor
Commencement Year
Advisor
Academic Affiliation
Non-Academic Affiliation
Subject
权利声明
Publisher
Peer Reviewed
Language
Digitization Specifications
  • File scanned at 300 ppi (Monochrome) using Capture Perfect 3.0 on a Canon DR-9050C in PDF format. CVista PdfCompressor 4.0 was used for pdf compression and textual OCR.
Replaces

关联

Parents:

This work has no parents.

属于 Collection:

单件

缩略图 标题 上传日期 公开度 行动
file details WangBingBing1998.pdf 2017-08-03 公开 下载