二苯二氯硅烷置于copper (II) Acetylacetonate体系中,用85%的收率获得产物叔丁基二苯基氯硅烷 参考文献:Process For The Preparation Of Silanes,With A Tertiary Hydrocarbon 标题:Process For The Preparation Of Silanes,With A Tertiary Hydrocarbon 摘要:本发明涉及一种制备一般式1 R.Sub.M R.Sup.1.Sub.N Six.Sub.4-M-N (1)的硅烷的方法,通过将一般式2 R.Sup.1 Mgx.Sup.1 (2)的grignard试剂与一般式3 R.Sub.M Six.Sub.4-M (3)的硅烷反应而得到,其中r表示c.Sub.1-C.Sub.10的碳氢基团,可选地被氟,氯或氰基团取代,R.Sup.1表示相对于硅原子的α位的三级c.Sub.4-C.Sub.30的碳氢基团,可选地被氟,氯或氰基团取代,X和x.Sup.1分别表示氯,溴或碘,M取值为2或3,N取值为1或2,在过渡金属催化剂和惰性,无质子,螯合化合物的存在下进行.
专利号:US-5849936-A 优先权日:1995-03-15 标题:Method for the synthesis of bis-tetrahydrofuranyl annonaceous acetogenins 发明人:HOYE THOMAS R; TAN LUSHI 权利人:UNIVERISTY OF MINNESOTA 摘要:A method for the synthesis of bis-tetrahydrofranyl Annonaceous acetogenins, including the natural products and analogs thereof, is provided which proceeds by the Pd-mediated coupling of a bis-tetrahydrofuranyl-subunit comprising a terminal alkyne, with a (C4)-hydroxybutenolide subunit comprising a terminal vinyl iodide, followed by selective reduction of the resulting enyne.
专利号:US-7589170-B1 优先权日:1998-09-25 标题 :Synthesis of cyclic peptides 发明人:SMYTHE MARK LESLIE; MEUTERMANS WIM DENIS FRANS; BOURNE GREGORY THOMAS; MCGEARY ROSS PETER 权利人:UNIV QUEENSLAND 摘要:This invention relates to methods for preparing cyclic peptides and peptidomimetic compounds in solution and bound to solid supports, and to cyclic peptide or peptidomimetic libraries for use in drug screening programs. In particular, the invention relates to a generic strategy for synthesis of cyclic peptides or peptidomimetics that enables the efficient synthesis under mild conditions of a wide variety of desired compounds. Two approaches were evaluated for their improvements in solution and solid phase synthesis of small cyclic peptides: positioning reversible N-amide substituents in the sequence; and applying native ligation chemistry in an intramolecular sense. Systematic investigation of the effects of preorganising peptides prior to cyclisation by using peptide cyclisation auxiliaries, and developing new linkers and peptide cyclisation auxiliaries to aid cyclic peptide synthesis gives surprising improvements in both yields and purity of products compared to the prior art methods. The combination of these technologies provides a powerful generic approach for the solution and solid phase synthesis of small cyclic peptides. The ring contraction and N-amide substitution technology of the invention provide improved methods for the synthesis of cyclic peptides and peptidomimetics. When used in conjunction with linker strategies, this combination provides solid-phase avenues to cyclic peptides and peptidomimetics.
专利号:US-7420052-B2 优先权日:2001-08-24 标 题:Intermediates for synthesis of vinblastine, process for preparation of the intermediates and process for synthesis of vinblastines 发明人:FUKUYAMA TOHRU; TOKUYAMA HIDETOSHI; YOKOSHIMA SATOSHI 权利人:JAPAN SCIENCE & TECH AGENCY 摘要:An intermediate for vinblastine synthesis represented by general formula A. n ngeneral formula A.n n(in the formula, R 1 , R 2 , R 3 and R 4 are the group selected independently from the group consisting of H, lower alkyl group, lower alkoxy group, halogen, lower perfluoroalkyl group, lower alkylthio group, hydroxy group, amino group, mono- or di-alkyl or acylamino group, lower alkyl or arylsulfonyloxy group. R 5 is H, or a lower alkyl group or a substituted or non-substituted aryl group, R 6 is an alkyl group of carbon number 4 or less, R 7 is a substituted or non-substituted aryl group, R 8 is a substituted or non-substituted aryl group or lower alkyl group and R 9 is an acyl group or trialkylsilyl group.) A method for synthesis of the compound of general formula A utilizing radical ring forming reaction of thioanilides and using the compound of general formula B as the starting material, synthesizing thioanilide of general formula C by the reaction with compound 1 and the formation of a 11-membered ring by intramolecular alkylation of 2-nitrobenzenesulfonamide by which the reactions can proceed under mild conditions and high yield can be accomplished.
专利号:US-4870199-A 优先权日:1986-04-30 标题 :Processes for the synthesis of diprotected R[R*,S*]-3,5-dihydroxy-6-oxohexanoate esters 发明人:CHEN KAU-MING; HARDTMANN GOETZ E; KAPA PRASAD K; LEE GEORGE T; LINDER JEROME; WATTANASIN SOMPONG 权利人:SANDOZ PHARMACEUTICALS CORP 摘要:Process for the synthesis of compounds of the formula in R[R*,S*] enantiomeric form, wherein each P1 is independently an hydroxy group-protecting group, and R2z is C1-4alkyl, benzyl or allyl, comprising, as a key step when R2z is R2x, the reaction of the compound of the formula in (S) enantiomeric form with a compound of the formula Mg &cir& +2 ((-)OOC-CH2-COOR2x)2 to obtain a compound of the formula in (S) enantiomeric form, and, as a key step when R2z is R2y, the reaction of a compound of the formula in (S) enantioimeric form with a compound of the formula Li(+)(-)CH2-COOR2y to obtain a compound of the formula in (S) enantiomeric form, wherein R2x is primary or secondary C1-4alkyl, benzyl or allyl, R2y is C1-4alkyl not containing an asymmetric carbon atom, and R3' is methyl or ethyl, processes for the synthesis of compounds of the formula comprising reacting a compound of the formula with the reaction product of a strong base and a compound of the formula optionally followed by, when R2z is allyl, cleavage of the allyl and P1 groups to obtain the corresponding compound of the formula wherein each R7 is methyl or ethyl, R is as defined in the specification, and each P1 independently and R2z are as defined above, and the compounds of the formula wherein R and each R7 are as defined above.
专利号:US-2018297925-A1 优先权日:2015-10-12 标题 :Methods for total synthesis of resolvin e1 发明人:JAGTAP PRAKASH 权利人:SALZMAN LOVELACE INVEST LTD 摘要:Methods for total chemical synthesis of Resolvin E1 (RvE1) include Wittig reaction of two compounds having hydroxyl protecting group in the presence of a strong base, removal of the hydroxyl-protecting groups with a deprotecting reagent to produce a compound having an ester group, and hydrolysis of the ester group to obtain RvE1
专利号:US-9783549-B2 优先权日:2013-11-04 标题:Macrocyclization reactions and intermediates useful in the synthesis of analogs of halichondrin B 发明人:FANG FRANCIS G; KIM DAE-SHIK; CHOI HYEONG-WOOK; CHASE CHARLES E; LEE JAEMOON 权利人:EISAI R&D MAN CO LTD 摘要:The invention provides methods for the synthesis of eribulin or a pharmaceutically acceptable salt thereof (e.g., eribulin mesylate) through a macrocyclization strategy. The macrocyclization strategy of the present invention involves subjecting a non-macrocyclic intermediate to a carbon-carbon bond-forming reaction (e.g., an olefination reaction (e.g., Homer-Wadsworth-Emmons olefination), Dieckmann reaction, catalytic Ring-Closing Olefin Metathesis, or Nozaki-Hiyama-Kishi reaction) to afford a macrocyclic intermediate. The invention also provides compounds useful as intermediates in the synthesis of eribulin or a pharmaceutically acceptable salt thereof and methods for preparing the same.
[参考文献]: Konstantina C Fylaktakidou, Et Al. Polyphosphates And Pyrophosphates Of Hexopyranoses As Allosteric Effectors Of Human Hemoglobin: Synthesis, Molecular Recognition, And Effect On Oxygen Release. Chemmedchem. 2011 Jan 3;6(1):153-68. [参考文献]: Maria Teresa Barros, Et Al. Regioselective Copolymerization Of Acryl Sucrose Monomers. J Org Chem. 2004 Oct 29;69(22):7772-5.
合成参考文献
参考文献:10.1007/978-1-61779-188-8_3 摘要:Hari Y, Kodama T, Imanishi T, Obika S. 2'-O,4'-C-methyleneoxymethylene bridged nucleic acids (2',4'-BNA(COC)). Methods Mol Biol. 2011;764():31–57. doi: 10.1007/978-1-61779-188-8_3.