Stereocontrol by Quaternary Centres: A Stereoselective Synthesis of (−)-Luminacin D

Very high diastereoselectivity can be achieved by 1,3‐chelation‐controlled allylation of aldehydes that possess a non‐chelating α‐ether substituent, even if the α‐position is a quaternary centre and/or a spiro‐epoxide. This reaction was used as a key step in an enantioselective synthesis of the angiogenesis inhibitor luminacin D. Control centre: Very high diastereoselectivity can be achieved by 1,3‐chelation‐controlled allylation of aldehydes that possess a non‐chelating α‐ether substituent, even if the α‐position is a quaternary centre and/or a spiro‐epoxide. This reaction was used as a key step in an enantioselective synthesis of the angiogenesis inhibitor luminacin D (see scheme).