title: A novel C,D-spirodioxene taxoid synthesized through an unexpected Pd-mediated ring cyclization.
abstract: A novel C,D-spirodioxene taxoid (6) was prepared from paclitaxel (1a), with the key steps including an unexpected Pd-mediated ring cyclization. The anti-tubulin activity of 6 was decreased relative to that of 1a and a previously reported C,D-spirolactone taxane (5). These observations could be rationalized on the basis of molecular modeling results. To the best of our knowledge, this is the first example indicating that 1,4-dioxenes can be synthesized from a mono-allyl vicinal diol through a Wacker-type cyclization. This strategy may be applicable to the synthesis of other C,D-spiro taxoids.
authors.affiliation: State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, 2A Nanwei Road, Beijing 100050, China. wfang@imm.ac.cn.
authors.forename: Shao-Rong
authors.initials: SR
authors.lastname: Wang
authors.affiliation: Área de Farmacología, Departamento de Ciencias Biomédicas, Universidad de Alcalá, E-28871 Alcalá de Henares, Unidad Asociada al Instituto de Química Médica del CSIC, E-28871 Madrid, Spain.
authors.forename: Pedro A
authors.initials: PA
authors.lastname: Sánchez-Murcia
authors.affiliation: Área de Farmacología, Departamento de Ciencias Biomédicas, Universidad de Alcalá, E-28871 Alcalá de Henares, Unidad Asociada al Instituto de Química Médica del CSIC, E-28871 Madrid, Spain.
authors.forename: Federico
authors.initials: F
authors.lastname: Gago
authors.affiliation: State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, 2A Nanwei Road, Beijing 100050, China. wfang@imm.ac.cn.
authors.forename: Wei-Shuo
authors.initials: WS
authors.lastname: Fang
mesh_terms: D003500:Cyclization; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D043823:Taxoids / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C000610868:C,D-spirodioxene taxoid; D043823:Taxoids; D010165:Palladium