Yan Bingli, Spilling Christopher D
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121-4499, USA.
J Org Chem. 2008 Jul 18;73(14):5385-96. doi: 10.1021/jo8004028. Epub 2008 Jun 17.
Palladium-catalyzed decarboxylative rearrangement of nonracemic phosphono allylic acetoacetates, or the intermolecular allylic substitution of nonracemic phosphono allylic carbonates with tert-butyl acetoacetate followed by hydrolysis and decarboxylation, gave omega-ketovinyl phosphonates. A highly regioselective Wacker oxidation gave the omega,beta-diketophosphonates which underwent intramolecular HWE reaction to give nonracemic cyclopentenones. An aldol condensation leading to phosphonocyclopentenones was competitive with the HWE reaction. The stereochemistry of the cyclopentenone and the ratio of HWE to aldol products were dependent upon the choice of base used in the reaction.
钯催化非外消旋膦酰基烯丙基乙酰乙酸酯的脱羧重排，或非外消旋膦酰基烯丙基碳酸酯与乙酰乙酸叔丁酯的分子间烯丙基取代，随后进行水解和脱羧反应，得到ω-酮乙烯基膦酸酯。高度区域选择性的瓦克氧化反应得到ω,β-二酮膦酸酯，其进行分子内HWE反应得到非外消旋环戊烯酮。导致膦酰基环戊烯酮的羟醛缩合反应与HWE反应相互竞争。环戊烯酮的立体化学以及HWE产物与羟醛产物的比例取决于反应中所用碱的选择。
