📜四苯基二膦置于titanium(Iv) Isopropylate,Sodium Hydroxide,三乙氧基硅烷,水,双(三甲基硅烷基)氨基钾体系中,化学反应 8.0H,反应生成 顺式-二苯乙烯 参考文献:Trans Stereoselectivity In The Reaction Of Cyclic Phosphonium Salts With Aromatic Aldehydes 标题:Trans Stereoselectivity In The Reaction Of Cyclic Phosphonium Salts With Aromatic Aldehydes 摘要:在磷鎓盐[rch2P(Ph)(Ch2)5]+br-中,磷原子被纳入一个六元环内,以此类雌鎓与取代芳香醛进行wittig烯化反应时,选择性地反应生成e型烯烃. DOI:10.1055/s-1998-1702
专利号:US-6794534-B2 优先权日:2000-06-23 标题:Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing metathesis 发明人:GRUBBS ROBERT H; CHATTERJEE ARNAB K; MORGAN JOHN P; SCHOLL MATTHIAS; CHOI TAE-LIM 权利人:CALIFORNIA INST OF TECHN 摘要:The invention is directed to the cross-metathesis and ring-closing metathesis reactions between geminal disubstituted olefins and terminal olefins, wherein the reaction employs a Ruthenium or Osmium metal carbene complex. Specifically, the invention relates to the synthesis of α-functionalized or unfunctionalized olefins via intermolecular cross-metathesis and intramolecular ring-closing metathesis using a ruthenium alkylidene complex. The catalysts preferably used in the invention are of the general formula n wherein: n M is ruthenium or osmium; n X and X 1 are each independently an anionic ligand; n L is a neutral electron donor ligand; and, n R, R 1 R 6 , R 7 , R 8 , and R 9 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl.
专利号:US-4895996-A 优先权日:1988-10-17 标 题 :Synthesis of alkenes from enamines via hydroboration 发明人:GORALSKI CHRISTIAN T; SINGARAM BAKTHAN; BROWN HERBERT C 权利人:PURDUE RESEARCH FOUNDATION; DOW CHEMICAL CO 摘要:Alkenes are prepared by the hydroboration of enamines followed by an elimination reaction to form the alkene. This process has wide applicability and is useful for the stereospecific synthesis of [Z] isomers. It is preferred to use 9-borabicyclo[3.3.1 nonane as the hydroborating agent and to use methanol to catalyze the elimination reaction.
专利号:US-7105695-B2 优先权日:2001-12-21 标题 :Synthesis of combretastatin A-2 prodrugs 发明人:PETTIT GEORGE R; MOSER BRYAN R 权利人:UNIV ARIZONA STATE 摘要:The original synthesis of combretastatin A-2 (1a) was modified to provide an efficient scale-up procedure for obtaining this antineoplastic stilbene. Subsequent conversion to a useful prodrug was accomplished by phosphorylation employing in situ formation of dibenzylchlorophosphite followed by cleavage of the benzyl ester protective groups with bromotrimethylsilane to afford phosphoric acid intermediate 11. The latter was immediately treated with sodium methoxide to complete a practical route to the disodium phosphate prodrug (2a). The phosphoric acid precursor (11) of phosphate 2a was employed in a parallel series of reactions to produce a selection of metal and ammonium cation prodrug candidates. Each of the phosphate salts (2a–q) was evaluated with respect to relative solubility behavior, cancer cell growth inhibition, and antimicrobial activity.
专利号:US-6316675-B1 优先权日:1997-03-25 标 题:Process for the preparation of an olefin-substituted aromatic or heteroaromatic compound 发明人:REETZ MANFRED T; LOHMER GUNTHER; LOHMER RENATE 权利人:STUDIENGESELLSCHAFT KOHLE MBH 摘要:A process for the synthesis of olefins having aromatic substituents is described in which olefins are reacted with aryl halides in the presence of catalysts consisting of palladium compounds and tetraaryl phosphonium salts.
专利号:US-6509506-B1 优先权日:1997-05-21 标 题 :Two step synthesis of D- and L- α-amino acids and D- and L- α-amino aldehydes 发明人:SHARPLESS K BARRY; LI GUIGEN 权利人:SCRIPPS RESEARCH INST 摘要:D- and L- α-amino acids and D- and L-α-amino aldehydes are synthesized from olefin substrates in two steps. The first step is a catalyzed asymmetric aminohydroxylation addition reaction to the olefin substrate. The addition reaction is catalyzed by osmium and is co-catalyzed by chiral ligands. The chiral ligands, in addition to being co-catalysts with the osmium, also serve to direct the addition reaction regioselectively and enantioselectively, divalent ligands are preferred over monovalent ligands because of their enhanced regio-and enantio-selectivity. As an oxidant nitrogen source for the addition reaction, either a carbamate or sulfonamide may be employed. If carbamate is employed as an oxidant nitrogen source, the resultant β-hydoxycarbamate is deprotected to yield the corresponding β-hydroxyamine. If sulfonamide is employed as an oxidant nitrogen source, the resultant β-hydroxysulfonamide is deprotected to yield the corresponding β-hydroxyamine. The resultant β-hydroxyamine is then selectively oxidized in a second synthetic step to produce the desired D- and L- α-amino acid or D- and L-α-amino aldehyde.
专利号:US-7705188-B2 优先权日:2002-04-10 标 题:Structural modification of resveratrol: sodium resverastatin phosphate 发明人:PETTIT GEORGE R; GREALISH MATTHEW P 权利人:UNIV ARIZONA 摘要:Described herein are novel compounds having antineoplastic and antimicrobial activity, obtained via structural modifications of resveratrol and combretastatin A-4, methods for synthesis of these compounds, and their use in pharmaceutical composition and for use in the treatment of mammals having cancer. Examples of the novel compounds are: (Z)- and (E)-3,4′,5-trimethoxystilbene (4a, 4b); (Z)- and (E)-3,5-dimethoxy-4′-hydroxystilbene (14c, 14d); (Z)- and (E)-3-hydroxy-4′,5-dimethoxystilbene (14g, 14h); (Z)- and (E)-3,5-dihydroxy-4′-methoxy-stilbene (14k, 14l); sodium resverastatin dibenzyl phosphate ((Z)-3,5-dimethoxy-4-[O-bis(benzyl)phosphoryl]-stilbene) (14m); and sodium resverastatin phosphate (14n).