Formal Total Synthesis of Oximidine II via a Suzuki-Type Cross-Coupling Macrocyclization Employing Potassium Organotrifluoroborates
作者:Gary A. Molander、Florian Dehmel
DOI:10.1021/ja047190o
日期:2004.8.1
A formal total synthesis of oximidineII has been achieved, employing a Suzuki-type coupling approach to construct the highly strained, polyunsaturated 12-membered macrolactone. To achieve this goal, benefit was derived from the stability of potassium alkenyltrifluoroborates to establish conditions for the macrocyclization. The stereocontrolled formation of the cis-1,2-diol subunit was accomplished
已经实现了肟 II 的正式全合成,采用 Suzuki 型耦合方法构建了高度应变的多不饱和 12 元大环内酯。为了实现这一目标,从烯基三氟硼酸钾的稳定性中获益,为大环化建立条件。顺式 1,2-二醇亚基的立体控制形成是使用 Carreira 方案使用非对映选择性、试剂控制添加到手性醛中来完成的。利用 Snieckus 硼氢化试剂获得大环化所需的关键三氟硼酸盐。
[EN] DERIVATIVES OF UNCIALAMYCIN, METHODS OF SYNTHESIS AND THEIR USE AS ANTITUMOR AGENTS<br/>[FR] DÉRIVÉS DE L'UNCIALAMYCINE, PROCÉDÉS DE SYNTHÈSE ET LEUR UTILISATION COMME AGENTS ANTI-TUMORAUX
申请人:UNIV RICE WILLIAM M
公开号:WO2015023879A1
公开(公告)日:2015-02-19
In one aspect, the present disclosure provides new analogs of uncialamycin of formulae (I) and (II). The present disclosure also provides novel synthetic pathways to obtaining uncialamycin and analogs thereof. Additionally, the present disclosure also describes methods of use of uncialamycin and analogs thereof. In another aspect, the present disclosure provides antibody-drug conjugates comprising the compounds of formulae (I) and (ll).
Setbacks and hopes: en route to the synthesis of uncialamycin
作者:Sandy Desrat、Mickael Jean、Pierre van de Weghe
DOI:10.1016/j.tet.2011.07.090
日期:2011.9
We herein report a new approach toward the synthesis of uncialamycin, an enediyne natural product isolated from the Streptomyces uncialis, bacteria present on the surface of the lichen Cladonia uncialis. A model for the preparation of uncialamycin has been achieved through a reaction cascade, an acetylide addition to the activated quinoline moiety, and a ring closure reaction as key steps.
Taxamycins: a new enediyne family constructed from versatile disilyl-substituted building blocks
作者:Yee Fung Lu、Curtis W. Harwig、Alex G. Fallis
DOI:10.1021/jo00068a011
日期:1993.7
The Pd(0)-based synthesis of two disilyl synthons [(Z)-1-(trimethylsilyl)-6-(tert-butyldiphenylsilyl)hex-3-ene-1,5-diyne (7) and (Z)-1-(trimethylsilyl)-6-(triisopropylsilyl)hex-3-ene-1,5-diyne (8)], selective removal of the trimethylsilyl group (K2CO3, MeOH) to afford 13 and 14, and the construction of the taxamycin-12 compound 25 (16,17,18-trimethyl-2-(monomethyloxy)-9-hydroxybicyclo[9.3.1]pentadec-5-ene-3,7-diyne) by intramolecular Nozaki condensation of the iodoalkyne 24 (1,3,3-trimethyl-2-(2-oxoethyl)-4-((Z)-1-(monomethyloxy)-7-iodohept-4-ene-3,6-diynyl)cyclohexene) is described.
Synthesis of Diynes and Tetraynes from in Situ Desilylation/Dimerization of Acetylenes
作者:Matthew A. Heuft、Shawn K. Collins、Glenn P. A. Yap、Alex G. Fallis
DOI:10.1021/ol016414u
日期:2001.9.1
[GRAPHICS]An efficient method for the in situ desillylation/oxidative dimerization of (trialkylsilyl)acetylenes is described. This protocol avoids the complications encountered with sensitive diynes by eliminating the deprotection and isolation steps. Various aromatic and alkyl diynes and tetraynes can be synthesized in a straightforward manner in good yields (82-99%) from TIPS-protected acetylenes. This method facilitates the efficient synthesis of novel tetrayne-bridged acetylenic cyclophanes 6 and 7 in a direct manner.