An expedited method was developed for the enantioselective synthesis of dodecahydrobenz[a]indolo[3,2-h]quinolizine containing five contiguous stereogenic centers with high enantioselectivities (>99% ee). The methodology comprises a domino organocatalytic double Michael reaction and Pictet-Spengler-lactamization reaction. The structures and absolute configurations of the appropriate products were confirmed by X-ray analysis.

An expedited method has been developed for the enantioselective synthesis of highly functionalized decaline systems containing seven contiguous stereogenic centers with high enantioselectivities (>99% ee). The one-pot methodology comprises a cascade of organocatalytic double Michael-photocatalyzed Michael-aldol reactions of ethyl 2-bromo-6-formylhex-2-enoate, β-alkyl-α,β-unsaturated aldehydes, and α-alkyl-α,β-unsaturated aldehydes. The structure and absolute configuration of an appropriate product were confirmed by X-ray analysis.

Sequential Asymmetric Catalysis in Michael-Michael-Michael-Aldol Reactions: Merging Organocatalysis with Photoredox Catalysis in a One-Pot Enantioselective Synthesis of Highly Functionalized Decalines Bearing a Quaternary Carbon Stereocenter. -Reaction of bromoacrylate (I) with cinnamic aldehyde (II) in the presence of diphenylsilylprolinol is optimized to yield a dialdehyde (III) produced by double Michael reaction. Subsequent photoredox-catalyzed Michael-Aldol reaction with ,-unsaturated aldehyde (IV) produces functionalized decalins (V) and (VI). The process is combined in a one-pot manner to provide optically active functionalized decalins (IX) in moderate yields. -(HONG*, B.-C.; LIN, C.-W.; LIAO, W.-K.; LEE, G.-H.; Org. Lett. 15 (2013) 24, 6258-6261, http://dx.doi.org/10.1021/ol403113c ; Dep. Chem. Biochem., Natl. Chung Cheng Univ., Chia-Yi 621, Taiwan; Eng.) -Mais 22-108