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A Dual-Catalysis Approach to Enantioselective [2 + 2] Photocycloadditions Using Visible Light

Science  25 Apr 2014:
Vol. 344, Issue 6182, pp. 392-396
DOI: 10.1126/science.1251511

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A Dual Approach to 2 + 2

Asymmetric catalysis generally accelerates the pathway to one specific product geometry that can be manipulated by reducing the temperature to slow down competing reactions. It is more difficult to be selective in photochemical reactions, but in the [2 + 2] coupling of olefins to make four-membered rings, Du et al. (p. 392; see the Perspective by Neier) used a ruthenium catalyst that absorbs visible light to activate the substrates below the frequency threshold where they absorb intrinsically. Then a second—a chiral Lewis acid—catalyst directs the product stereochemistry. A major advantage of the dual reactions is that each catalyst can be tuned independently.

Abstract

In contrast to the wealth of catalytic systems that are available to control the stereochemistry of thermally promoted cycloadditions, few similarly effective methods exist for the stereocontrol of photochemical cycloadditions. A major unsolved challenge in the design of enantioselective catalytic photocycloaddition reactions has been the difficulty of controlling racemic background reactions that occur by direct photoexcitation of substrates while unbound to catalyst. Here, we describe a strategy for eliminating the racemic background reaction in asymmetric [2 + 2] photocycloadditions of α,β-unsaturated ketones to the corresponding cyclobutanes by using a dual-catalyst system consisting of a visible light–absorbing transition-metal photocatalyst and a stereocontrolling Lewis acid cocatalyst. The independence of these two catalysts enables broader scope, greater stereochemical flexibility, and better efficiency than previously reported methods for enantioselective photochemical cycloadditions.

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