Author Type

Graduate Student

Date of Award

2005

Document Type

Thesis

Publication Status

Version of Record

Submission Date

October 2026

Abstract

We report here the development of an efficient method for the conversion of a variety of conjugated alkynyl esters to alpha-substituted conjugated allenyl esters (racemic) through the use of strong amide bases. Substantially improved yields over typical enolate formation conditions were observed with the use of two equivalents of lithium diisopropylamide. Trapping studies indicate that the second equivalent of base likely leads to the dianion intermediate which upon addition of methyl iodide and trimethylsilyl chloride gives mixtures of alpha-substituted conjugated allenyl and beta,gamma-alkynyl deconjugated esters. Further optimization revealed that additive salts such as LiCl lead primarily to the allenyl product while the use of HMPA as a cosolvent gives the beta,gamma-alkynyl deconjugated alkylation product. The role of base, base concentration and electrophile on product yield and selectivity is also discussed. The optimized conditions resulting from our study of this reaction establishes this method as a viable synthetic tool for the production of alpha-substituted allenyl esters. A new method to prepare racemic alpha-tributylstannyl-alpha-allenyl esters from precursor conjugated alkynyl esters in good yields is reported. Key features of the optimized reaction conditions include the use of multiple equiv. of lithium diisopropylamide in THF with LiCl as a key additive. The allenyl tin reagent reacts with aldehydes in the presence of Lewis acid to give homopropargyl alcohol or allenyl alcohol products depending on the reaction conditions. The addition of boron trifluoride etherate to a solution of the allenyltin and aldehyde gives the homopropargyl alcohol. However, allenyl alcohol products are obtained exclusively with the addition of tin tetrachloride to the allenyl stannane rapidly followed by the addition of aldehyde. The effect of other Lewis acids and reaction variables such as solvent and temperature on the yield and relative stereochemistry of the products will also be described. The Mitsunobu coupling reaction of sterically hindered phenols and alcohols is greatly accelerated by the use of high reaction concentration in combination with sonication. The rate acceleration effect observed with our protocol may simply be based on the high concentration with the sonic waves providing efficient mixing of the highly viscous reaction mixture and generating localized hot spots, or in part, the result of an enhancement of a radical reaction pathway.

Extent

216 p.

Comments

FAU Electronic Theses and Dissertations Collection|Adviser: Salvatore D. Lepore.|Thesis (Ph.D.)--Florida Atlantic University, 2005.|FAU Electronic Theses and Dissertations Collection

Identifier

FADT12120

Format

pdf

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