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:US-5266708-A 优先权日:1989-12-01 标题 :New intermediates, process for their preparation, and their use for the synthesis of vitamins A and E 发明人:CHABARDES PIERRE F; DUHAMEL LUCETTE; DUHAMEL PIERRE; GUILLEMONT JEROME; POIRIER JEAN-MARIE 权利人:RHONE POULENC NUTRITION ANIMAL 摘要:New intermediates and processes for the preparation of vitamins A and E, which are the acetals of 5,6-dihalo-3-methyl-3-hydroxyhexanal or of 6-halo-3-hydroxy-3-methyl-5-hexenal or 3-methyl-3-hydroxy-5-hexenal, as well as processes for making the intermediates. After dehydrohalogenation and dehydration these intermediates are condensed directly with β-ionone or with 2-methyl-2-heptene-6-one to synthesize vitamins A and E respectively.
专利号:US-5120864-A 优先权日:1989-12-01 标 题:Intermediates, process for their preparation, and their use for the synthesis of vitamins a and e 发明人:CHARBARDES PIERRE F; DUHAMEL LUCETTE; DUHAMEL PIERRE; GUILLEMONT JEROME; POIRIER JEAN-MARIE 权利人:RHONE POULENC NUTRITION ANIMAL 摘要:New intermediates and processes for the preparation of vitamins A and E, which are the acetals of 5,6-dihalo-3-methyl-3-hydroxyhexanal or of 6-halo-3-hydroxy-3-methyl-5-hexenal or 3-methyl-3-hydroxy-5-hexenal, as well as processes for making the intermediates. After dehydrohalogenation and dehydration these intermediates are condensed directly with β-ionone or with 2-methyl-2-heptene-6-one to synthesize vitamins A and E respectively.
专利号:EP-0432021-A1 优先权日:1989-12-01 标题 :Intermediates, procedure for their preparation and their use in the synthesis of vitamins A and E
专利号:WO-9316022-A1 优先权日:1992-02-05 标题 :Palladium catalyzed alkylative cyclization useful in synthesis of vitamin d and analogues
参考标题:Ring Strain And Total Syntheses Of Modified Macrocycles Of The Isoplagiochin Type 作者:Andreas Speicher,Timo Backes,Kerstin Hesidens,Jürgen Kolz 摘要:Macrocycles Of The Bisbibenzyl-Type Are Natural Products That Are Found Exclusively In Bryophytes (Liverworts). The Molecular Framework Of The Subtype "Isoplagiochin" Is Of Substantial Structural Interest Because Of The Chirality Of The Entire Molecule, Which Arises From Two Biaryl Axes In Combination With Two Helical Two-Carbon Units In A Cyclic Arrangement. From A Structural As Well As A Synthetic Point Of View We Report On The Total Synthesis Of Compounds Which Possess More Rigid Two-Carbon Biaryl Bridges Like Stilbene (E Or Z) Or Even Tolane Moieties Which Were Introduced Starting With A Sonogashira Protocol. The Mcmurry Method Proved To Be A Powerful Tool For The Cyclization To These Considerably Ring-Strained Macrocycles.
合成参考文献
摘要:Broggini, G.; Borsini, E.; Piarulli, U., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2012) 3, 570.