A dual-catalysis approach to enantioselective [2 + 2] photocycloadditions using visible light.
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.
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
Juana
J
Du
Kazimer L
KL
Skubi
Danielle M
DM
Schultz
Tehshik P
TP
Yoon
D002384:Catalysis; D061565:Cycloaddition Reaction / Q000379:methods*; D003503:Cyclobutanes / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry; D008027:Light; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D055668:Photochemical Processes; D013237:Stereoisomerism
D003503:Cyclobutanes; D007659:Ketones; D058116:Lewis Acids; D009942:Organometallic Compounds; C415768:tris(2,2'-bipyridyl)ruthenium(II)