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Synlett 2003(10): 1379-1390
DOI: 10.1055/s-2003-40817
DOI: 10.1055/s-2003-40817
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York
In Search of an Atom-Economical Synthesis of Chiral Ynamides
Jason A. Mulder, Kimberly C. M. Kurtz, Richard P. Hsung*Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA
e-Mail: hsung@chem.umn.edu;
Weitere Informationen
Publikationsverlauf
Received
10 March 2003
Publikationsdatum:
24. Juli 2003 (online)
Abstract
Failed attempts and successes in searching for an atom-economical and efficient synthesis of chiral ynamides are described in this account. These events are illustrated in chronological order, and comparisons are made along the way to reflect other elegant methods known for preparations of ynamides and other electron deficient ynamines. The purpose of this account is to facilitate and revitalize interest in the chemistry of ynamines within the synthetic community.
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1 Introduction
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2 Failed Attempts in Achieving Direct Approaches
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2.1 Palladium Catalyzed Cross-Coupling
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2.2 Alkynyl Iodonium Salts
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2.3 Base-Promoted Isomerization
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3 Elimination Protocols
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3.1 Lithium-Halogen Exchange
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3.2 The Viehe Sequence
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4 The Isomerization Protocol with Limitations
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5 A Cu-Salt Catalyzed Cross-Coupling
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6 Summary
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7 Outlook
Key words
Ynamines - electron deficient ynamines - ynamides - base-promoted isomerization of propargyl amides - copper catalyzed cross-couplings of amides - alkynyl halides
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The unfortunate and premature loss of Professor J. Ficini is one critical reason for lack of advancement in the field.
10No real attempt is being made in this account to truly distinguish or classify various different electron deficient ynamines 1-9 in Figure [2] , however, for certain level of structural clarity and convenience we have regarded compounds 1-5 as electron deficient ynamines whereas compounds 6-9 in which the nitrogen atom is directly attached to an electron-withdrawing carbonyl or sulfonyl group as ynamides.