Efforts Toward a Unified Kainoid Family Synthesis Approach

Unexpected Sulfinamide-Directed Conjugate Addition Results

Isaac Chogii, Pradipta Das, Jon T Njardarson

Research output: Contribution to journalArticle

Abstract

A short asymmetric synthesis of an all-syn and all-trans kainoid core is reported. The synthetic route relies on the application of a new asymmetric [3+2] annulation reaction followed by a conjugate addition reaction to install this kainoid's three stereocenters. A surprising intramolecular conjugate addition enabled by the chiral tert-butylsulfinyl group residing on the 3-pyrroline nitrogen atom surpassed its expected role as a steric spectator. Efforts to outcompete intramolecular 1,4-addition by further oxidizing the sulfoxide, or use of additives, and advancement of the all-syn addition product to the requisite kainoid common core are detailed.

Original languageEnglish (US)
JournalAsian Journal of Organic Chemistry
DOIs
StatePublished - Jan 1 2019

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sulfoxide
Addition reactions
Nitrogen
Atoms
pyrroline

Keywords

  • anionic cascade
  • annulation
  • asymmetry
  • kainic acid
  • sulfonamide

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Efforts Toward a Unified Kainoid Family Synthesis Approach: Unexpected Sulfinamide-Directed Conjugate Addition Results",
abstract = "A short asymmetric synthesis of an all-syn and all-trans kainoid core is reported. The synthetic route relies on the application of a new asymmetric [3+2] annulation reaction followed by a conjugate addition reaction to install this kainoid's three stereocenters. A surprising intramolecular conjugate addition enabled by the chiral tert-butylsulfinyl group residing on the 3-pyrroline nitrogen atom surpassed its expected role as a steric spectator. Efforts to outcompete intramolecular 1,4-addition by further oxidizing the sulfoxide, or use of additives, and advancement of the all-syn addition product to the requisite kainoid common core are detailed.",
keywords = "anionic cascade, annulation, asymmetry, kainic acid, sulfonamide",
author = "Isaac Chogii and Pradipta Das and Njardarson, {Jon T}",
year = "2019",
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language = "English (US)",
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AU - Das, Pradipta

AU - Njardarson, Jon T

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N2 - A short asymmetric synthesis of an all-syn and all-trans kainoid core is reported. The synthetic route relies on the application of a new asymmetric [3+2] annulation reaction followed by a conjugate addition reaction to install this kainoid's three stereocenters. A surprising intramolecular conjugate addition enabled by the chiral tert-butylsulfinyl group residing on the 3-pyrroline nitrogen atom surpassed its expected role as a steric spectator. Efforts to outcompete intramolecular 1,4-addition by further oxidizing the sulfoxide, or use of additives, and advancement of the all-syn addition product to the requisite kainoid common core are detailed.

AB - A short asymmetric synthesis of an all-syn and all-trans kainoid core is reported. The synthetic route relies on the application of a new asymmetric [3+2] annulation reaction followed by a conjugate addition reaction to install this kainoid's three stereocenters. A surprising intramolecular conjugate addition enabled by the chiral tert-butylsulfinyl group residing on the 3-pyrroline nitrogen atom surpassed its expected role as a steric spectator. Efforts to outcompete intramolecular 1,4-addition by further oxidizing the sulfoxide, or use of additives, and advancement of the all-syn addition product to the requisite kainoid common core are detailed.

KW - anionic cascade

KW - annulation

KW - asymmetry

KW - kainic acid

KW - sulfonamide

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