Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides

Ommidala Pattawong, Darlene Q. Tan, James C. Fettinger, Jared T. Shaw, Paul Ha Yeon Cheong

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Computations (SCS-MP2//B3LYP) reveal that the asymmetric synthesis of highly substituted γ-lactams with three stereogenic centers, including one quaternary center, proceeds through a Mannich reaction between the enol form of the anhydride and the E-imine, followed by a transannular acylation. This new mechanistic picture accounts for both the observed reactivity and stereoselectivity. CH-O and hydrogen bonding interactions in the Mannich step and torsional steering effects in the acylation step are responsible for stereocontrol. It is demonstrated that this new mechanistic picture applies to the related reactions of homophthalic anhydrides with imines and presents new vistas for the design of a new reaction to access complex molecular architectures.

Original languageEnglish (US)
Pages (from-to)5130-5133
Number of pages4
JournalOrganic Letters
Volume15
Issue number19
DOIs
StatePublished - Oct 4 2013

Fingerprint

Lactams
Acylation
Imines
Anhydrides
anhydrides
imines
acylation
Stereoselectivity
Hydrogen Bonding
synthesis
Hydrogen bonds
reactivity
methylidyne
hydrogen
interactions

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Biochemistry

Cite this

Pattawong, O., Tan, D. Q., Fettinger, J. C., Shaw, J. T., & Cheong, P. H. Y. (2013). Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides. Organic Letters, 15(19), 5130-5133. https://doi.org/10.1021/ol402561q

Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides. / Pattawong, Ommidala; Tan, Darlene Q.; Fettinger, James C.; Shaw, Jared T.; Cheong, Paul Ha Yeon.

In: Organic Letters, Vol. 15, No. 19, 04.10.2013, p. 5130-5133.

Research output: Contribution to journalArticle

Pattawong, O, Tan, DQ, Fettinger, JC, Shaw, JT & Cheong, PHY 2013, 'Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides', Organic Letters, vol. 15, no. 19, pp. 5130-5133. https://doi.org/10.1021/ol402561q
Pattawong, Ommidala ; Tan, Darlene Q. ; Fettinger, James C. ; Shaw, Jared T. ; Cheong, Paul Ha Yeon. / Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides. In: Organic Letters. 2013 ; Vol. 15, No. 19. pp. 5130-5133.
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