(+)-5-ethyl-1,4,5,8-tetrahydro-5-hydroxy-7-iodo-8-(3-tert-butyldimethylsilyl-2-propynyl)oxepino[3,4-c]pyridine-3,9-dione | 472958-53-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (+)-5-ethyl-1,4,5,8-tetrahydro-5-hydroxy-7-iodo-8-(3-tert-butyldimethylsilyl-2-propynyl)oxepino[3,4-c]pyridine-3,9-dione
• 英文别名: (5R)-8-[3-[tert-butyl(dimethyl)silyl]prop-2-ynyl]-5-ethyl-5-hydroxy-7-iodo-1,4-dihydrooxepino[3,4-c]pyridine-3,9-dione
• CAS: 472958-53-5
• 化学式: C₂₀H₂₈INO₄Si
• 分子量: 501.437
• InChiKey: FRFMONKLDZNCIY-HXUWFJFHSA-N

物化性质

• 沸点：
  608.1±55.0 °C(predicted)
• 密度：
  1.43±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.55
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-5-ethyl-1,4,5,8-tetrahydro-5-hydroxy-7-iodo-8-(3-tert-butyldimethylsilyl-2-propynyl)oxepino[3,4-c]pyridine-3,9-dione 在 偶氮二异丁腈 、 水 、 三正丁基氢锡 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 11.0h， 生成 (R)-10-hydroxy-7-(tert-butyldimethylsilyl)homocamptothecin
  参考文献：
  名称：

  Asymmetric total synthesis of (20R)-homocamptothecin, substituted homocamptothecins and homosilatecans

  摘要：

  An efficient asymmetric synthesis of a key DE lactone pyridone intermediate in the synthesis of homocamptothecin is reported. The synthesis is scalable and features a Stille coupling and a Sharpless asymmetric epoxidation as the key steps. The key intermediate has been parleyed into homocamptothecin and an assortment of fluorinated homocamptothecins and homosilatecans (7-silylhomocamptothecins), thereby providing the first asymmetric entry to this important new class of antitumor agents. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00632-4
• 作为产物：
  描述：

  (-)-3-hydroxy-3-[2-methoxy-3-methoxymethoxymethyl-6-(trimethylsilanyl)pyridin-4-yl]pentanoic acid 在 三甲基氯硅烷 、 水 、 一氯化碘 、 sodium hydride 、 三氟乙酸 、 sodium iodide 、 lithium bromide 作用下， 以 四氯化碳 、 乙二醇二甲醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 65.0h， 生成 (+)-5-ethyl-1,4,5,8-tetrahydro-5-hydroxy-7-iodo-8-(3-tert-butyldimethylsilyl-2-propynyl)oxepino[3,4-c]pyridine-3,9-dione
  参考文献：
  名称：

  Asymmetric total synthesis of (20R)-homocamptothecin, substituted homocamptothecins and homosilatecans

  摘要：

  An efficient asymmetric synthesis of a key DE lactone pyridone intermediate in the synthesis of homocamptothecin is reported. The synthesis is scalable and features a Stille coupling and a Sharpless asymmetric epoxidation as the key steps. The key intermediate has been parleyed into homocamptothecin and an assortment of fluorinated homocamptothecins and homosilatecans (7-silylhomocamptothecins), thereby providing the first asymmetric entry to this important new class of antitumor agents. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00632-4

文献信息

• [EN] SYNTHESIS OF POLYCYCLIC QUINOLINES<br/>[FR] SYNTHESE DE QUINOLINES POLYCYCLIQUES
  申请人：UNIV PITTSBURGH

  公开号：WO2003099825A1

  公开（公告）日：2003-12-04

  A method of synthesizing a polycyclie quinoline comprising the step of a cascade annulation wherein the precursor is reacted with an aryl isonitrile having the formula in the presence of a transition metalwherein X is chlorine, bromine, iodine or triflate; wherein R1, R2, R3 and R4 are independently the same or different and are hydrogen, -OR wherein R is H, an alkyl group, an aryl goup or a hydroxy protecting group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyloxy group, an acylamino group, a nitro group, a cyano group, -OC(O)ORa, wherein Ra is an alkyl group or an aryl group, -NRbRC wherein Rb and Rc are independently the same or different, H, an alkyl group, an aryl group or an amino protecting group, -OC(O)NRbRC, -C(O)Rd wherein Rd is H, an alkyl group, an aryl group, an alkoxy group, or -NRbRC, -SR, wherein Re is an alkyl group or an aryl group, -OSiRe3, or R1 and R2 or R2 and R3 together form a chain of three or four members selected from the group of CH, CH2, O, S, NH, of NRf, wherein Rf is an C1-C6 alkyl group; wherein R5 is cyano, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, -C(O)Rd wherein Rd is H, an alkyl group, an aryl group, an alkoxy group, -NRb RC, or -Si(RgRhRi)..or -(Rj)Si(RgRhRi), wherein Rj is an alkylene group, an alkenylene group, or an alkynylene group; and R6, Rh and Ri are independently a C1-10 alkyl group, a C2-10 alkenyl group, a C2-10 alkynyl group, or an aryl group; wherein R6 is H, F, Cl, a C1-3 alkyl group, a C2-3 alkenyl group, a C2-3 alkynyl group, a trialkylsilyl group or a C1-3 alkoxy group; and wherein R7 and R8 are independently the same or different and are H, F, Cl, an alkyl group, an aryl group, a hydroxyalkyl group, a dialkylamino alkyl group, or wherein R7 and R8 together form a chain of four or five members selected from the groups -C(Rk)(OR1)(CH2)ZC(O)OCH2- wherein z is an integer between 0 and 1, wherein Rk is H, an alkyl group, an allyl group, a propargyl group or a benzyl group, Rl is H, -C(O)Rd wherein Rd is H, an alkyl group, an aryl group, an alkoxy group, -NRbRc or -Si(RmRnRo) wherein Rm, Rn and Ro are independently a C1-10 alkyl group, a C2-10 alkenyl group, a C2-10 alkynyl group, or an aryl group..

  一种合成多环喹啉的方法，包括级联环化步骤，其中在过渡金属的存在下，前体与具有以下式的芳基异腈反应，其中X为氯、溴、碘或三氟甲磺酸盐；其中R1、R2、R3和R4独立地相同或不同，可以是氢、-OR，其中R为H、烷基、芳基或羟基保护基、烷基、芳基、烯基、炔基、酰氧基、酰胺基、硝基、氰基、-OC（O）ORa，其中Ra为烷基或芳基，-NRbRC，其中Rb和Rc独立地相同或不同，可以是氢、烷基、芳基或氨基保护基，-OC（O）NRbRC，-C（O）Rd，其中Rd为H、烷基、芳基、烷氧基或-NRbRC，-SR，其中Re为烷基或芳基，-OSiRe3，或R1和R2或R2和R3一起形成从CH、CH2、O、S、NH或NRf组成的三个或四个成员的链，其中Rf为C1-C6烷基；其中R5为氰基、烷基、芳基、烯基、炔基、-C（O）Rd，其中Rd为H、烷基、芳基、烷氧基、-NRbRC或-Si（RgRhRi）..或-（Rj）Si（RgRhRi），其中Rj为烷基、烯基或炔基；且R6、Rh和Ri独立地为C1-10烷基、C2-10烯基、C2-10炔基或芳基，其中R6为H、F、Cl、C1-3烷基、C2-3烯基、C2-3炔基、三烷基硅基或C1-3烷氧基；且R7和R8独立地相同或不同，可以是H、F、Cl、烷基、芳基、羟基烷基、二烷基氨基烷基，或其中R7和R8一起形成从-C（Rk）（OR1）（ ）ZC（O）O -中选择四个或五个成员的链，其中z为0到1的整数，其中Rk为H、烷基、烯丙基、丙炔基或苄基，Rl为H、-C（O）Rd，其中Rd为H、烷基、芳基、烷氧基、-NRbRc或-Si（RmRnRo），其中Rm、Rn和Ro独立地为C1-10烷基、C2-10烯基、C2-10炔基或芳基。
• Palladium-Promoted Cascade Reactions of Isonitriles and 6-Iodo-<i>N</i>-propargylpyridones:  Synthesis of Mappicines, Camptothecins, and Homocamptothecins
  作者：Dennis P. Curran、Wu Du

  DOI：10.1021/ol026408d

  日期：2002.9.1

  Ambient-temperature reactions of electron-rich aryl isonitriles with substituted 6-iodo-N-propargylpyridones in the presence of silver carbonate and palladium acetate produce 11H-indolizino[1,2b]quinolin-9-ones in good to excellent yield. Experimental evidence suggests that the process coccurs though organopalladium rather than radical intermediates. It is applied to synthesis analogues of mappicine and camptothecin, including the silatecans DB-67 and DB-91 (homo-DB-67).