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Ketone-imide versus ketone-oxime reductive cross-coupling promoted by samarium diiodide: new mechanistic insight gained from a failed aminocyclopentitol synthesis.

[reaction: see text] The intramolecular 1,6-ketone/imide reductive coupling promoted by samarium diiodide competes favorably with an alternative 1,5-ketone/oxime ether coupling in a keto-oxime substrate derived from D-glucosamine N-protected with a phthalimido group. This pinacol coupling reaction affords new homochiral alpha-hydroxylactam scaffolds that could be useful in diversity-oriented synthesis. A mechanistic proposal for this reaction that explains the experimental results is supported by DFT quantum-mechanical calculations on model compounds.

Cyclization↗

Ketones in resin composites. Effect of ketone content and monomer composition on selected mechanical properties.

To optimize the improvements by diketones of the mechanical properties of resin composites, diacetyl was added to two different monomer mixtures in different quantities. There was a positive correlation between content of diacetyl and tensile strength, flexural strength, and modulus of elasticity, respectively, of both the BISGMA/TEGDMA- and the UEDMA/HEMA-based materials. Addition of diacetyl did not influence the modulus of resilience significantly. Addition of diacetyl resulted in increases in mechanical properties which were of the same relative size for BISGMA/TEGMA-based materials as for UEDMA/HEMA-based materials. However, because of higher control values, except for modulus of elasticity, the properties of UEDMA/HEMA-based composites were superior to those of the BIGSMA/TEGDMA-based materials. A content of approximately 24 mole% diacetyl seemed to have optimum effect on mechanical properties, giving a mean increase of 25% in tensile strength, flexural strength, and modulus of elasticity.

Analysis of Variance↗