Addition 8-phenylmenthyl acrylate

Phenylmenthyl acrylate has been used as a component in an asymmetric Baylis-Hillman reaction. Treatment of the acrylate with 1,4-Diazabicyclo[2.2.2]octane and benzaldehyde at 8 kbar of pressure delivers the a-(hydroxyalkyl)acrylate (eq 8). The product obtained has an 86% de. Menthyl acrylate is superior to the phenylmenthyl acrylate in this particular application. In a radical-mediated addition, phenylmenthyl acrylate gives rise to the a-pyridyl sulfide in 68% yield (eq 9). The final product is isolated with a 56% de. 

In an asymmetric approach to the bicyclo[2.2.2]octane ring system, a double Michael addition has been employed using phenylmenthyl acrylate as the initial Michael acceptor. The condensation of the dienolate, generated with Lithium Diisopropylamide, reacts with the acrylate to afford the bicyclo[2.2.2]octane derivative (eq 6). The de for the reaction is only 50% however, it is highly endo selective (>95%). ... 

A Lewis acid-mediated two-fold asymmetric Michael addition allows access to c( s-decalin derivatives. The reaction of the trimethylsilylenol ether of acety Icyclohexene with phenylmenthyl acrylate in the presence of Diethylaluminum Chloride (eq 7) yields the decalone in 64% yield (70% de). This has been shown not to be a Diels-Alder reaction. If the reaction is worked-up early, the initial Michael adduct can be isolated. ... 

Simpler, open-chain, chiral alkenes have also been employed in [3 + 2]-cycloaddition reactions in order to obtain face selectivity of the addition. The introduction of chiral alcohols such as ( —)-(l/ ,27 ,5S)-menthol into acrylic esters provides a simple entry into this field however, the conformational variability of such molecules allows for only relatively low stereoselectivities.The same is true for the (— )-(l /J,2i ,4i )-bornyl and (— )-(l 7 ,27 ,55)-8-phenylmenthyl derivatives. ... 

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