Extending Pummerer reaction chemistry. Development of a strategy for the regio- and stereoselective oxidative cyclization of 3-(ω-nucleophile)- tethered indoles

Ken S. Feldman, Daniela Boneva Vidulova, Andrew G. Karatjas

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

The brominative cyclization of diastereomeric β-silyloxy tryptophan derivatives proceeded with divergent regiochemistry (C(2) or C(3) addition), depending on the relative stereochemistry of the silyloxy substituent. This lack of C(2) vs C(3) regiochemical predictability led to the development of a new approach, which featured Pummerer-type chemistry on an indole C(2) sulfoxide or sulfide substrate, for steering nucleophilic addition to C(3) of the indole. Extension of this transformation from carboxylate nucleophiles to carbon analogues such as allylsilane, silyl enol ether, and silyl ketene iminal bearing substrates led to the formation of spirocyclic oxindole derivatives in good yields with complete regioselectivity for C(3) cyclization and with good diastereoselectivity where relevant.

Original languageEnglish (US)
Pages (from-to)6429-6440
Number of pages12
JournalJournal of Organic Chemistry
Volume70
Issue number16
DOIs
StatePublished - Aug 5 2005

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Indoles
Nucleophiles
sulfoxide
Cyclization
Bearings (structural)
Derivatives
Regioselectivity
Stereochemistry
Sulfides
Substrates
Tryptophan
Ether
Carbon
indole
ketene
allylsilane
oxindole

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

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abstract = "The brominative cyclization of diastereomeric β-silyloxy tryptophan derivatives proceeded with divergent regiochemistry (C(2) or C(3) addition), depending on the relative stereochemistry of the silyloxy substituent. This lack of C(2) vs C(3) regiochemical predictability led to the development of a new approach, which featured Pummerer-type chemistry on an indole C(2) sulfoxide or sulfide substrate, for steering nucleophilic addition to C(3) of the indole. Extension of this transformation from carboxylate nucleophiles to carbon analogues such as allylsilane, silyl enol ether, and silyl ketene iminal bearing substrates led to the formation of spirocyclic oxindole derivatives in good yields with complete regioselectivity for C(3) cyclization and with good diastereoselectivity where relevant.",
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Extending Pummerer reaction chemistry. Development of a strategy for the regio- and stereoselective oxidative cyclization of 3-(ω-nucleophile)- tethered indoles. / Feldman, Ken S.; Vidulova, Daniela Boneva; Karatjas, Andrew G.

In: Journal of Organic Chemistry, Vol. 70, No. 16, 05.08.2005, p. 6429-6440.

Research output: Contribution to journalArticle

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