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. 2017 Sep 18;56(39):11891-11895.
doi: 10.1002/anie.201706975. Epub 2017 Aug 30.

Enantioselective Crossed Photocycloadditions of Styrenic Olefins by Lewis Acid Catalyzed Triplet Sensitization

Zachary D Miller  1 , Byung Joo Lee  1 , Tehshik P Yoon  1
Affiliations

Enantioselective Crossed Photocycloadditions of Styrenic Olefins by Lewis Acid Catalyzed Triplet Sensitization

Zachary D Miller et al. Angew Chem Int Ed Engl. .

Abstract

The synthesis of unsymmetrical cyclobutanes by controlled heterodimerization of olefins remains a substantial challenge, particularly in an enantiocontrolled fashion. Shown herein is that chiral Lewis acid catalyzed triplet sensitization enables the synthesis of highly enantioenriched diarylcyclobutanes by photocycloaddition of structurally varied 2'-hydroxychalcones with a range of styrene coupling partners. The utility of this reaction is demonstrated through the direct synthesis of a representative norlignan cyclobutane natural product.

Keywords: asymmetric catalysis; cycloaddition; cyclobutanes; photocatalysis; ruthenium.

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Figures

Figure 1
Figure 1
Representative cyclobutane natural products.
Figure 2
Figure 2
Representative cyclobutane scaffolds accessible by enantioselective [2+2] cycloaddition.
Scheme 1
Scheme 1
Proposed mechanism of cycloadditions featuring Lewis acid catalysed triplet sensitization.
Scheme 2
Scheme 2
Synthesis of norlignan cyclobutane 3: a. 2.5 mol% Ru(bpy)3(PF6)2, 32 mol% Sc(OTf)3, 38 mol% (S,S)-tBuPybox, 12 h, 23 W CFL. b. NH3, MeOH/THF, 12 h; then NaOCl, THF, 30 min. c. NaOH, H2O/EtOH, 95 °C, 36 h. d. MeI, K2CO3, DMF, 1 h. e. 10 mol% RockPhos G3 precatalyst, 2.0 equiv Cs2CO3, 5.0 equiv MeOH, PhMe, 90 °C, 24 h.
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