عنوان

General Approach to the Synthesis of the Chlorosulfolipids Danicalipin A, Mytilipin A, and Malhamensilipin A in Enantioenriched Form and Progress towards the Synthesis of the Psammaplysin Family of Natural Products

Number

TL94s970ss

.Language of Text, Soundtrack etc

انگلیسی

Title Proper

General Approach to the Synthesis of the Chlorosulfolipids Danicalipin A, Mytilipin A, and Malhamensilipin A in Enantioenriched Form and Progress towards the Synthesis of the Psammaplysin Family of Natural Products

General Material Designation

[Thesis]

First Statement of Responsibility

Carlson, Joseph Scott

Subsequent Statement of Responsibility

Vanderwal, Christopher D

Date of Publication, Distribution, etc.

2015

Body granting the degree

Vanderwal, Christopher D

Text preceding or following the note

2015

Text of Note

The dissertation describes a second-generation synthesis of three structurally related chlorosulfolipid natural products. Chapter 1 of the dissertation focuses on the discovery and state of the synthetic art of the chlorosulfolipids at the time this work began. Chapter 2 of the dissertation describes the key advances made, include highly stereocontrolled additions to α,β-dichloroaldehydes, kinetic resolutions of complex vinyl epoxide intermediates, and Z-selective cross metatheses of vinyl epoxides. Chapter 3 of the dissertation describes background information pertaining to the psammaplysin family of natural products, including their biosynthesis and relevant bioactivity. Also described is the retrosynthetic strategy developed for the synthesis of all members of the psammaplysin family of natural products, featuring a donor-acceptor cyclopropane fragmentation as the key step. Chapter 4 details the exploration of several strategies designed to evaluate the best methods for: incorporation of the secondary stereogenic alcohol, donor-acceptor cyclopropane fragmentation/spirocyclic ring formation, and oximinoamide incorporation. A ketene Diels-Alder disconnection strategy was successful in producing the spirooxepin-isoxazoline ring fusion present in the psammaplysin family of natural products. Also described are preliminary results for incorporation of the stereogenic alcohol at an early stage intermediate that has the potential for being elaborated further using the ketene Diels-Alder strategy.

Hu, Kun

Carlson, Joseph Scott

UC Irvine

Electronic name

p

[Thesis]

276903

a

Y