专利号:US-5292977-A 优先权日:1992-02-05 标题:Palladium catalyzed alkylative cyclization useful in synthesis of vitamin D and analogues 发明人:TROST BARRY M; DUMAS JACQUES 权利人:UNIV LELAND STANFORD JUNIOR 摘要:An alkylative cycloaddition method is provided that is particularly useful for the synthesis of many of the Vitamin D analogues with differing side chains. Thus, a preferred synthesis is of Vitamin D analogues having a side chain R 1 where a substantially geometrically pure first precursor having the structure ##STR1## and a second precursor are provided, the second precursor being a 1,7 enyne. These precursors are reacted in the presence of a palladium catalyst to form compounds having the structure ##STR2## where R 2 hydrogen, hydroxyl, lower alkoxy, fluorine, or a protecting group, and R 3 is hydrogen, hydroxyl, lower alkoxy, fluorine, or a protecting group.
专利号:US-5446225-A 优先权日:1992-02-05 标题:Palladium catalyzed akylative cyclization useful in syntheses of Vitamin D and analogues 发明人:TROST BARRY M; DUMAS JACQUES 权利人:UNIV LELAND STANFORD JUNIOR 摘要:An alkylative cycloaddition method is provided that is particularly useful for the synthesis of many of the Vitamin D analogues with differing side chains. Thus, a preferred synthesis is of Vitamin D analogues having a side chain R 1 where a first precursor having the structure ##STR1## with X being a halide or a pseudo halide, and a second precursor are provided, the second precursor being a 1,7 enyne. These precursors are reacted in the presence of a palladium catalyst to form compounds having the structure ##STR2## where R 2 is hydrogen, hydroxyl, lower alkoxy, fluorine, or a protecting group, and R 3 is hydrogen, hydroxyl, lower alkoxy, fluorine, or a protecting group.
专利号:EP-1494680-B1 优先权日:2002-03-25 标题 :Use of carbon-2-modified-vitamin d analogs to induce the formation of new bone 发明人:DELUCA HECTOR F; PIKE J WESLEY; SHEVDE NIRUPAMA K 权利人:WISCONSIN ALUMNI RES FOUND 摘要:It has been discovered that the 2-carbon-modified derivatives of 1α,25-dihydroxyvitamin D3 specifically stimulate osteoblasts to form new bone. The ability of the 2-carbon-modified vitamin D analogs to stimulate new bone formation suggest that these compounds can be used where synthesis of new bone is required. Thus, these compounds can be used either systemically or locally to stimulate the growth of bone transplants, to increase the rate of fracture healing and thereby reduce the time required for the healing of fractures, the stimulation of bone growth when required for replacement surgery, and also for the growth of bone to implants or other devices required to maintain the skeleton or teeth in the proper positions.
专利号:CA-2561590-C 优先权日:2004-04-02 标题 :Novel method for the preparation of intermediates useful for the synthesis of vitamin d analogues
专利号:WO-2005095336-A2 优先权日:2004-04-02 标 题 :Novel method for the preparation of intermediates useful for the synthesis of vitamin d analogues
专利号:EP-1735276-A2 优先权日:2004-04-02 标题:Novel method for the preparation of intermediates useful for the synthesis of vitamin d analogues
参考文献:10.1016/j.bmcl.2012.05.037 摘要:DeBerardinis AM, Banerjee U, Miller M, Lemieux S, Hadden MK. Probing the structural requirements for vitamin D3 inhibition of the hedgehog signaling pathway. Bioorganic & Medicinal Chemistry Letters. 2012 Jul;22(14):4859–63. doi: 10.1016/j.bmcl.2012.05.037.