Organocatalytic Diastereoselective (4 + 1) Cycloaddition of o -Hydroxyphenyl-Substituted Secondary Phosphine Oxides.

The first organocatalytic diastereoselective (4 + 1) cycloaddition of o -hydroxyphenyl-substituted secondary phosphine oxides (SPOs) has been established, which makes use of o -hydroxyphenyl substituted SPOs as suitable four-atom phosphorus-containing 1,4-dinucleophiles and 3-indolylformaldehydes as competent 1,1-dielectrophiles under Bro̷nsted acid catalysis. The reaction mechanism was suggested to involve the formation of 3-indolylmethanol intermediates and vinyliminium intermediates, which played an important role in controlling the reactivity and diastereoselectivity of the (4 + 1) cycloaddition under Bro̷nsted acid catalysis. By this approach, a series of benzo oxaphospholes bearing P - and C -stereocenters were synthesized in moderate to good yields (50%-95% yields) with excellent diastereoselectivities (all >95:5 dr). This reaction not only represents the first organocatalytic diastereoselective (4 + 1) cycloaddition of o -hydroxyphenyl-substituted SPOs but also provides an efficient and diastereoselective method for the construction of phosphorus-containing benzo five-membered heterocyclic skeletons bearing both P -stereocenter and C -stereocenter.