Stereoselective photodimerization of SnCl4 complexes of cyclic α,β-unsaturated ketones in the solid state

Photochemistry, bearing significant applications in natural and man-made events such as photosynthesis, vision, photolithography, photodynamic therapy, etc., is yet to become a common tool during the synthesis of small molecules in a laboratory. Among other rationale, the inability to influence photochemical reactions with temperature, solvent, additives, etc., dissuades chemists from employing light-initiated reactions as a routine synthetic tool. This review highlights how diverse, highly organized structures such as solvent-free crystals and water-soluble host-guest assemblies can be employed to control and manipulate photoreactions and thereby serve as an efficient tool for chemists, including those interested in synthesis. The efficacy of the media in modifying the excited-state behavior of organic molecules is illustrated with photocycloaddition in general and [2 + 2] photocycloaddition in particular, reactions widely employed in the synthesis of complex natural products as well as highly constrained molecules, as exemplars. The reaction media, highly pertinent in the context of green sustainable chemistry, include solvent-free crystals and solids such as silica, clay, and zeolite and water-soluble hosts that can solubilize and preorganize hydrophobic reactants in water. Since no other reagent would be more sustainable than light and no other medium greener than water, we believe that the supramolecular photochemistry expounded here has a momentous role as a synthetic tool in the future.

show abstract

Origins of Selectivity for the [2+2] Cycloaddition of α,β-unsaturated Ketones within a Porous Self-assembled Organic Framework

Yang

Dewal

Profeta

et al. 2007

J. Am. Chem. Soc.

View full text Add to dashboard Cite

X-Ray Structure Determination, C 12 H 16 O 2 X-ray diffraction intensity data from a colorless plate crystal were measured at 150(1) K using a Bruker SMART APEX diffractometer (Mo K radiation, = 0.71073 Å). 1 Raw area detector data frame integration was performed with SAINT+. 1 Final unit cell parameters were determined by least-squares refinement of 2964 strong reflections from the data set. Direct methods structure solution, difference Fourier calculations and full-matrix least-squares refinement against F 2 were performed with SHELXTL. 2 The compound crystallizes in the space group P2 1 /n as determined uniquely by the pattern of systematic absences in the intensity data. The asymmetric unit consists of half of one molecule located on a crystallographic inversion center. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were located in difference maps

show abstract

Stereoselective photodimerization of SnCl4 complexes of cyclic α,β-unsaturated ketones in the solid state

Cited by 5 publications

References 13 publications

[2 + 2]‐ Photocycloadditions in the Solid State

[2 + 2]‐ Photocycloadditions in the Solid State

Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition

Origins of Selectivity for the [2+2] Cycloaddition of α,β-unsaturated Ketones within a Porous Self-assembled Organic Framework

Contact Info

Product

Resources

About