(4R,5S,6S)-4-(2-Benzyloxy-ethyl)-6-iodomethyl-5-methyl-[1,3]dioxan-2-one | 137664-73-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4R,5S,6S)-4-(2-Benzyloxy-ethyl)-6-iodomethyl-5-methyl-[1,3]dioxan-2-one
• 英文别名: (4S,5S,6R)-4-(iodomethyl)-5-methyl-6-(2-phenylmethoxyethyl)-1,3-dioxan-2-one
• CAS: 137664-73-4
• 化学式: C₁₅H₁₉IO₄
• 分子量: 390.218
• InChiKey: UJMIFDMBVBHSJI-IACUBPJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  tert-butyl [(3R,4R)-4-methyl-1-phenylmethoxyhex-5-en-3-yl] carbonate 在 一溴化碘 作用下， 以 甲苯 为溶剂， 生成 (4R,5S,6R)-4-(2-Benzyloxy-ethyl)-6-iodomethyl-5-methyl-[1,3]dioxan-2-one 、 (4R,5S,6S)-4-(2-Benzyloxy-ethyl)-6-iodomethyl-5-methyl-[1,3]dioxan-2-one
  参考文献：
  名称：

  (+)-Calyculin A 和 (-)-Calyculin B 的全合成：C(9-25) Spiroketal Dipropionate 亚基的不对称合成

  摘要：

  描述了花萼 (1-8) 的立体化学完全赋予的 C(9-25) spiroketal 片段 (+)-BC 的不对称合成。合成的亮点包括：高度非对映选择性 IBr 诱导的碘碳酸酯环化以在环氧化物 (+)-18 中引入 C(21) 立体中心，片段结合利用酰基阴离子等价物与环氧化物的反应构建掩蔽的高级醛醇 (-)- 35 和 (+)-71 作为单一非对映异构体，将 C(14−15) 乙烯基螯合控制加成到醛 (+)-38 以将立体异构性设置为 C(16)，选择性还原 C(13)酮通过 1,3 诱导，以及正交保护方案的开发，允许 C(17) 磷酸基团的方便安装和随后片段耦合的灵活性。

  DOI：

  10.1021/ja992134m

文献信息

• Iodine monobromide (IBr) at low temperature: A superior protocol for diastereoselective cyclizations of homoallylic carbonates
  作者：James J.-W. Duan、Paul A. Sprengeler、Amos B. Smith

  DOI：10.1016/s0040-4039(00)79009-5

  日期：1992.10

  Iodine monobromide (IBr) induces efficient electrophilic cyclizations of homoallylic t-butyl carbonates in toluene or methylene chloride al low temperature, affording significantly better diastereoselectivity than iodine (I2) in acetonitrile.
• Iodine monobromide (IBr) at low temperature: enhanced diastereoselectivity in electrophilic cyclizations of homoallylic carbonates
  作者：James J. W. Duan、Amos B. Smith

  DOI：10.1021/jo00066a024

  日期：1993.7

  Iodine monobromide affords superior diastereoselectivity in low-temperature electrophilic cyclizations of homoallylic carbonates. Solvent and temperature effects and the scope and limitations of the method are discussed; optimal selectivity is obtained in toluene at -80 to -85-degrees-C. The latter protocol generally furnishes significantly enhanced selectivity, vis-a-vis the original procedure employing 12 in acetonitrile at -20-degrees-C; for example, the IBr-induced cyclization of 14 affords a 25.8:1 mixture of 15 and 16, whereas I2 gives an 8.4:1 ratio. An equilibration experiment established that the diastereoselectivity derives primarily or exclusively from kinetic control of the cyclization process.
• Calyculin synthetic studies. Stereoselective construction of the C(14)-C(25) spiroketal subunit
  作者：Amos B. Smith、James J.-W. Duan、Kenneth G. Hull、Brian A. Salvatore

  DOI：10.1016/s0040-4039(00)93479-8

  日期：1991.9

  A convergent, stereocontrolled synthesis of the spiroketal fragment of calyculins A-H has been achieved. Key transformations include the novel iodine monobromide-induced iodocarbonate cyclization of (+)-19, efficient coupling of epoxide (+)-14 with the sterically hindered dithiane 15, and a multi-step, one-pot conversion of open-chain precursor (-)-13 to spiroketal (+)-11.
• Total Synthesis of (+)-Calyculin A and (−)-Calyculin B:  Asymmetric Synthesis of the C(9−25) Spiroketal Dipropionate Subunit
  作者：Amos B. Smith、Gregory K. Friestad、Joseph Barbosa、Emmanuel Bertounesque、Kenneth G. Hull、Makoto Iwashima、Yuping Qiu、Brian A. Salvatore、P. Grant Spoors、James J.-W. Duan

  DOI：10.1021/ja992134m

  日期：1999.11.1

  An asymmetric synthesis of the stereochemically fully endowed C(9−25) spiroketal fragment (+)-BC of the calyculins (1−8) is described. Highlights of the synthesis include: a highly diastereoselective IBr-induced iodocarbonate cyclization to introduce the C(21) stereocenter in epoxide (+)-18, fragment unions exploiting the reaction of acyl anion equivalents with epoxides to construct masked advanced

  描述了花萼 (1-8) 的立体化学完全赋予的 C(9-25) spiroketal 片段 (+)-BC 的不对称合成。合成的亮点包括：高度非对映选择性 IBr 诱导的碘碳酸酯环化以在环氧化物 (+)-18 中引入 C(21) 立体中心，片段结合利用酰基阴离子等价物与环氧化物的反应构建掩蔽的高级醛醇 (-)- 35 和 (+)-71 作为单一非对映异构体，将 C(14−15) 乙烯基螯合控制加成到醛 (+)-38 以将立体异构性设置为 C(16)，选择性还原 C(13)酮通过 1,3 诱导，以及正交保护方案的开发，允许 C(17) 磷酸基团的方便安装和随后片段耦合的灵活性。