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    • 1. 发明申请
    • METHODS FOR NUCLEOPHILIC FLUOROMETHYLATION
    • 用于核酸氟代甲基化的方法
    • WO2004063129A2
    • 2004-07-29
    • PCT/US2004/000651
    • 2004-01-13
    • UNIVERSITY OF SOUTHERN CALIFORNIAPRAKASH, Surya, G., K.HU, JinboOLAH, George, A.
    • PRAKASH, Surya, G., K.HU, JinboOLAH, George, A.
    • C07C
    • C07D307/42C07C29/38C07C319/14C07C2603/74C07C323/03C07C33/46C07C31/38C07C35/52
    • A novel, convenient and efficient method for trifluoromethylation of substrate compounds is disclosed. Particularly, alkoxide and hydroxide induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides and other electrophiles, using phenyl trifluoromethyl sulfone PhSO2CF3 (or sulfoxide PhSOCF3) is disclosed. A method of both symmetrical and unsymmetrical anti-2,2-difluoropropan-1,3-diols with high diastereoselectivity (up to 94 % de) is disclosed using dufluoromethyl phenyl sulfone. This unusual type of high diastereoselectivity was obtained via an intramolecular charge-charge repulsion effect rather than the traditional steric control (based on the Cram's rule). Thus, difluoromethyl phenyl sulfone can be used as a novel difluoromethylene dianion species (`CF2""), which can couple two electrophiles (such as diphenyl disulfide or non-enolizable aldehydes) to give new difluoromethylenated products.
    • 公开了一种用于底物化合物三氟甲基化的新颖,方便和有效的方法。 特别地,公开了使用苯基三氟甲基砜PhSO 2 CF 3(或亚砜PhSOCF 3)的羰基化合物,二硫化物和其它亲电子体的醇盐和氢氧化物的亲核三氟甲基化。 使用二氟甲基苯基砜公开了具有高非对映选择性(高达94%de)的对称和不对称的2,2-二氟丙-1,3-二醇的方法。 这种不寻常类型的高非对映选择性通过分子内电荷 - 排斥效应而不是传统的空间控制获得(基于Cram的规则)。 因此,二氟甲基苯基砜可以用作新的二氟亚甲基二阴离子物质(“CF2”“),其可以偶合两种亲电子试剂(例如二苯基二硫化物或不可烯化的醛)以产生新的二氟亚甲基化产物。