Dissertation/Thesis Abstract

Allenes, Alkenes & Alkynes: My Piece of the π …in Water at Room Temperature…
by Lippincott, Daniel John, Ph.D., University of California, Santa Barbara, 2018, 545; 10982306
Abstract (Summary)

I. An environmentally responsible, mild method for the synthesis of functionalized 1,3-butadienes is presented. It utilizes allenic esters of varying substitution patterns, as well as a wide range of boron-based nucleophiles under palladium catalysis, generating sp–sp2, sp2–sp 2, and sp2–sp3 bonds. Functional group tolerance measured via robustness screening, along with room temperature and aqueous reaction conditions highlight the methodology’s breadth and potential utility in synthesis.

II. A mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patterns, along with a wide range of boron and alkenyl nucleophiles that couple under palladium catalysis leading to sp-, sp 2-, and sp3-substituted arrays. Regioselective transformations of the newly formed unsymmetrical dendralene derivatives are demonstrated. The use of micellar catalysis, where water is the global reaction medium, and room temperature reaction conditions, highlights the green nature of this technology.

III. A copper-catalyzed oxidative cleavage of electron-rich olefins into their corresponding carbonyl derivatives is described as an alternative to ozonolysis. The scope includes various precursors to aryl ketone derivatives, as well as oxidations of enol ethers bearing atypical alkyl and dialkyl substitution, the first of their kind among such metal catalyzed alkene cleavage reactions. The use of an inexpensive copper salt, room temperature conditions, an aerobic atmosphere, and water as the global reaction medium highlight the green features of this new method. Associated mechanistic investigations are also presented.

Indexing (document details)
Advisor: Lipshutz, Bruce H.
Commitee: Aue, Donald H., Hayton, Trevor W., Zakarian, Armen
School: University of California, Santa Barbara
Department: Chemistry
School Location: United States -- California
Source: DAI-B 80/07(E), Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Chemistry, Organic chemistry
Keywords: Alkenes, Alkynes, Allenes, Pi, Room temperature, Water
Publication Number: 10982306
ISBN: 9780438897366
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