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New Methods in Alkylidenecarbene Chemistry: A Mild Route to Cycloalkynes

thesis
posted on 01.08.2021, 00:00 by Panagiotis Dimitrios Alexakos
While the strain-accelerated cycloaddition of cyclooctynes has played a central role in the development of biomolecule conjugation and a range of related technologies, the preparation of these highly reactive alkynes remains challenging. In this context, we report an efficient, two-step method for the synthesis of cyclooctynes from cycloheptanones by way of 5-hydroxyalkyl-1H-tetrazoles. Treatment of these substrates with carbodiimide reagents leads to the formation and 1,2-rearrangement of a putative alkylidenecarbene intermediate generating the desired products in good to excellent yield. This ring expansion strategy displays broad substrate scope and functional group tolerance and is performed under mild, non-basic conditions. Details of this methodology and its application to the synthesis of a range of cyclooctynes, both stable and transient will be described.

History

Advisor

Wardrop, Duncan J

Chair

Wardrop, Duncan J

Department

Chemistry

Degree Grantor

University of Illinois at Chicago

Degree Level

Doctoral

Degree name

PhD, Doctor of Philosophy

Committee Member

Mohr, Justin T Miller, Lawrence Cologna, Stephanie Moore, Terry

Submitted date

August 2021

Thesis type

application/pdf

Language

en

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