Modern organic synthesis《近代有机合成》精美PPT.ppt

It is believed that the more reactive carbonyl group is protected as the hydrate, which is stabilized by complexation with the cerium ion, and is regenerated during the isolation of the product. ? Selective reduction of aldehydes in the presence of ketones can be effected with nBu4NB(OAc)3H and LiAlH[OC(C2H5)3]3. ? ? ? Reduction of ketones with an asymmetric center next to the carbonyl group ?? Cram’s rule (the conformation of the carbonyl compound in the transition state is determined by steric factors) ?? Cram’s rule may not be followed in case where there is a polar group on the carbon adjacent to the carbonyl group. ??? ?-hydroxy and ?-amino ketones The reaction is thought to proceed through a relatively rigid chelate compound. Therefore, reduction of ?-hydroxy and ?-amino ketones usually proceeds with a comparatively high degree of stereoselectivity. ??? ?-halo ketones The polar halogen atom and the polar carbonyl are anti disposed to minimize dipole-dipole repulsion. The hydride anion attacks from the less hindered side of the conformation. ? When the reducing agent itself is chiral and asymmetric reduction of unsymmetrical (prochiral) ketones to optically active secondary alcohols can often be achieved even when the ketones themselves are achiral. Other chiral complex hydrides: ? Reduction of cyclic ketones In general , a mixture of products is obtained. With comparatively unhindered kentones the more stable equatorial alcohol predominates, with hindered ketones the axial alcohol is the main product. Solutions of sodium in liquid ammonia also cleave aryl ethers. This is one of the few available methods for removal of the oxygen from a phenolic ring. Enols are similarly converted into alkenes ? Other deoxygenation methods The above–described method might not always be suitable, espically with polyfunctional compounds . Alternative methods to meet such cases have been developed. Primary and secondary alcohols can a