Rhodium‐Catalyzed Enantioselective Intramolecular [4+2] Cycloaddition using a Chiral Phosphine‐Phosphite Ligand: Importance of Microwave‐Assisted Catalyst Conditioning

The use of modular α,α,α′,α′‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol (TADDOL)‐ and 1,1′‐bi‐2‐naphthol (BINOL)‐derived phosphine‐phosphite ligands (L 2 *) in the asymmetric rhodium‐catalyzed intramolecular [4+2] cycloaddition (“neutral” Diels–Alder reaction) of ( E , E )‐1,6,8‐decatriene derivatives (including a 4‐oxa and a 4‐aza analogue) was investigated. Initial screening of a small ligand library led to the identification of a most promising, TADDOL‐derived ligand bearing a phenyl group adjacent to the phosphite moiety at the arene backbone. In the course of further optimization studies, the formation of a new, more selective catalyst species during the reaction time was observed. By irradiating the pre‐catalyst with microwaves prior to substrate addition high enantioselectivities (up to 93% ee ) were achieved. The new cyclization protocol was successfully applied to all three substrates investigated to give the bicyclic products in good yield and selectivity. 31 P NMR and ESI‐MS measurements indicated the formation of a [Rh(L 2 *) 2 ] + species as the more selective (pre‐) catalyst.