TANDEM BENZANNULATION-CYCLIZATION STRATEGIES FOR THE SYNTHESIS OF HIGHLY SUBSTITUTED INDOLES
Name
Faialaga-faialaga-phd-chemistry-2023-thesis.pdf
Description
Thesis PDF
Size
18.55 MB
Format
Adobe PDF
Checksum (MD5)
1430b14356d9a5188f311c0736505448
Author(s)
Faialaga, Nathan H.
Advisor(s)
Danheiser, Rick L.
Date Issued
February 2023
Publisher
Massachusetts Institute of Technology
Abstract
Tandem benzannulation-cyclization strategies were developed for the synthesis of highly substituted indoles. The benzannulation strategies involved the reaction of vinylketenes (or aryl ketenes) with ynamides or with ynehydrazides to afford highly substituted phenols via a pericyclic cascade mechanism. The vinylketenes were generated via the Wolff rearrangement of diazo enones or via the 4π electrocyclic ring-opening of cyclobutenones. Two cyclization approaches were studied: (1) an intramolecular acid-promoted cyclization, and (2) a Fischer indole cyclization. The first approach required the development of a thermal benzannulation protocol and was applied in a concise total synthesis of (-)-herbindoles A-C and (+)-trans-herbindole A. The second approach required the development of a new benzannulation variant that employed ynehydrazides as the ketenophile.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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