Experiments Directed Towards the Synthesis of Anthracyclinones. XXXIV Hetero-Diels–Alder Reactions Using Chiral Boron and Titanium Reagents

Abstract

Reactions between benzaldehyde or o-anisaldehyde and a series of silyloxy dienes catalysed by the chiral acyl- oxyborane (CAB) complex (4) give high yields of enantioselective products from a Mukaiyama aldol rather than a hetero-Diels–Alder reaction. Attempts to effect a similar catalytic reaction with anthraquinone aldehydes were unsuccessful but use of 2 equiv. of the CAB complex (1) followed by cyclization promotes a formal hetero- Diels–Alder reaction between the aldehyde (7) and the diene (12) to give the dihydropyrone (24) in 45% yield and with a 79% e.e. in favour of the 2'R enantiomer.

Hetero-Diels–Alder reactions between the aldehyde (7) and the diene (12) using the chiral titanium complexes Ti[(R)-BINOL]Cl ₂ , Ti[(R,R)-TADDOL]Cl ₂ and Ti[(R)-BINOL] ₂ have been investigated. The first two complexes promote the reaction at −30 and −78° respectively but with low induced enantioselectivities.