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. 2010 Mar 19;12(6):1152-5.
doi: 10.1021/ol902821w.

Torquoselective ring closures of chiral amido trienes derived from allenamides. A tandem allene isomerization-pericyclic ring-closure-intramolecular Diels-Alder cycloaddition

Ryuji Hayashi  1 , John B Feltenberger, Richard P Hsung
Affiliations

Torquoselective ring closures of chiral amido trienes derived from allenamides. A tandem allene isomerization-pericyclic ring-closure-intramolecular Diels-Alder cycloaddition

Ryuji Hayashi et al. Org Lett. .

Abstract

A new torquoselective ring-closure of chiral amide-substituted 1,3,5-hexatrienes and its application in tandem with [4 + 2] cycloaddition are described. The trienes were derived via either a 1,3-H or 1,3-H-1,7-H shift of alpha-substituted allenamides, and the entire sequence through the [4 + 2] cycloaddition could be in tandem from allenamides.

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Figures

Figure 1
Figure 1
A Torquoselective Disrotatory-Ring Closure.
Figure 2
Figure 2
X-Ray Structure of 31b.
Scheme 1
Scheme 1
A New Torquoselective Pericyclic Ring-Closure.
Scheme 2
Scheme 2
Complication with the 1,5-H Shift into Conjugation.
Scheme 3
Scheme 3
An Unexpected Competing 1,7-H Shift.
Scheme 4
Scheme 4
A Directional Preference in the 1,7-H Shift.
Scheme 5
Scheme 5
A Diverging Tandem Pathway: E- vs. Z-Olefin.
Scheme 6
Scheme 6
In Tandem with [4 + 2] Cycloaddition.
See this image and copyright information in PMC

References

    1. Hayashi R, Hsung RP, Feltenberger JB, Lohse AG. Org Lett. 2009;11:2125. - PMC - PubMed

    1. For reviews on chemistry of dienamides, see: Overman LE. Acc Chem Res. 1980;13:218.Petrzilka M. Synthesis. 1981:753.Campbell AL, Lenz GR. Synthesis. 1987:421.Also see: Krohn K. Angew Chem Int Ed Engl. 1993;32:1582.Enders D, Meyer O. Liebigs Ann. 1996:1023.

    1. For a review on the synthesis of enamides, see: Tracey MR, Hsung RP, Antoline J, Kurtz KCM, Shen L, Slafer BW, Zhang Y. In: Science of Synthesis, Houben-Weyl Methods of Molecular Transformations. Weinreb Steve M., editor. Chapter 21.4. Georg Thieme Verlag KG; 2005. For a leading review on recent chemistry of enamides, see: Carbery DR. Org Biomol Chem. 2008;9:3455.Rappoport Z. The Chemistry of Enamines in The Chemistry of Functional Groups; New York: John Wiley and Sons; 1994.

    1. For a leading review on allenamide chemistry, see: Hsung RP, Wei LL, Xiong H. Acc Chem Res. 2003;36:773.

    1. For recent reports on allenamide chemistry in 2009, see: Hashimoto K, Horino Y, Kuroda S. Heterocycles. 2010;80:187.Persson AKÅ, Johnston EV, Bäckvall JE. Org Lett. 2009;11:3817.Skucas E, Zbieg JR, Krische MJ. J Am Chem Soc. 2009;131:5054.Armstrong A, Emmerson DPG. Org Lett. 2009;11:1547.Beccalli EM, Broggini G, Clerici F, Galli S, Kammerer C, Rigamonti M, Sottocornola S. Org Lett. 2009;11:1563.Broggini G, Galli S, Rigamonti M, Sottocornola S, Zecchi G. Tetrahedron Lett. 2009;50:1447.Lohse AG, Hsung RP. Org Lett. 2009;11:3430.Lu T, Hayashi R, Hsung RP, DeKorver KA, Lohse AG, Song Z, Tang Y. Organic Biomol Chem. 2009;9:3331.

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