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. 2013 May 17;15(10):2514-7.
doi: 10.1021/ol400989x. Epub 2013 May 6.

A highly stereoselective addition of lithiated ynamides to Ellman-Davis chiral N-tert-butanesulfinyl imines

Xiao-Na Wang  1 , Richard P Hsung, Rui Qi, Sierra K Fox, Ming-Can Lv
Affiliations

A highly stereoselective addition of lithiated ynamides to Ellman-Davis chiral N-tert-butanesulfinyl imines

Xiao-Na Wang et al. Org Lett. .

Abstract

A highly diastereoselective addition of lithiated ynamides to Ellman-Davis chiral imines is described. While additions of N-sulfonyl ynamides are highly stereoselective even without Lewis acids, the use of BF3-OEt2 completely reversed the stereoselectivity. In addition, oxazolidinone-substituted ynamides behaved differently and functioned better with BF3-OEt2, and the chirality of the oxazolidinone ring exerts no impact on the selectivity.

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Figures

Figure 1
Figure 1
X-Ray Structure of 15-S.
Figure 2
Figure 2
Chelation-TS Versus Open-TS.
Figure 3
Figure 3
Effects of the Sulfonyl Substitutions.a,b a. Isolated Yields. b. Ratios determined by 1H and/or 13C NMR.
Scheme 1
Scheme 1
Approaches to Chiral γ–Amino-Ynamides.
Scheme 2
Scheme 2
Initial Assessment of The Two Approaches.
Scheme 3
Scheme 3
Reexamining the Addition of Ynamide 10.
Scheme 4
Scheme 4
Matching-Mismatching with Chiral Ynamide 7.
See this image and copyright information in PMC

References

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