(2S,3R)-4-(p-bromobenzyloxy)-2,3-epoxybutan-1-ol | 108267-97-6

• 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: (2S,3R)-4-(p-bromobenzyloxy)-2,3-epoxybutan-1-ol
• 英文别名: [(2S,3R)-3-[(4-bromophenyl)methoxymethyl]oxiran-2-yl]methanol
• CAS: 108267-97-6
• 化学式: C₁₁H₁₃BrO₃
• 分子量: 273.126
• InChiKey: PECBWSBCNVSTRY-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  42
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R)-4-(p-bromobenzyloxy)-2,3-epoxybutan-1-ol 在 偶氮二甲酸二异丙酯 、 silica gel 、 三苯基膦 作用下， 以 四氢呋喃 、 溶剂黄146 、 甲苯 为溶剂， 反应 98.0h， 生成 [(2S,3R)-3-acetyloxy-2-acetylsulfanyl-4-[(4-bromophenyl)methoxy]butyl] acetate
  参考文献：
  名称：

  Synthesis of [4,5-Bis(hydroxymethyl)-1,3-oxathiolan-2-yl]nucleosides as Potential Inhibitors of HIV via Stereospecific Base-Induced Rearrangement of a 2,3-Epoxy Thioacetate¹

  摘要：

  The synthesis of [4,5-bis(hydroxymethyl)-1,3-oxathiolan-2-yl]nucleosides is described. 2,3-Epoxy alcohol 10 was converted in one pot into thioacetate 11. Treatment of 11 under mild alkaline conditions gave thiirane 12 with inversion of configuration at C-2. We also found that thioacetate 11 rearranges into thiirane 14 under mild acidic conditions. This rearrangement reaction was shown by independent synthesis to proceed with net retention of configuration at C-2. We have proposed a tentative mechanism which may explain the results obtained. Opening of thiiranes 12; and 14 followed by deprotection gave (2R,3R)-2-thiothreitol (23) and (2S,3R)-2-thioerythritol (25), respectively. Regioselective silylation of the primary hydroxyl groups of 23 followed by treatment with trimethyl orthoformate gave 2-methoxy-1,3-oxathiolanes 26 and 27. Condensation with silylated baser followed by deprotection and separation of the anomers gave the oxathiolanyl-nucleosides. Compounds 29-31, 34, and 35 were found to be inactive when tested for inhibition of HIV-1 activity in vitro.

  DOI：

  10.1021/jo960009c
• 作为产物：
  描述：

  对溴溴苄 在 4 A molecular sieve titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二异丙酯 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 35.0h， 生成 (2S,3R)-4-(p-bromobenzyloxy)-2,3-epoxybutan-1-ol
  参考文献：
  名称：

  Rhizoxin D的全合成，Rhizoxin D是一种来自真菌Rhizopus chinensis的有效抗有丝分裂剂。

  摘要：

  根霉菌素D（2）由分别代表C3-C9，C10-C13，C14-C19和C20-C27的四个亚基A，B，C和D合成。亚基A是通过碘代乙缩醛21的环化制备的，该碘代乙缩醛21通过在（Z）-α，β-不饱和酯的β碳上立体选择性地添加衍生自21的脱卤基团而将C5的构型设定为2。乙醛29从苯硫缩醛24中获得，并在代表Wittig的Wittig反应中与代表亚基B的磷烷30缩合。该酯被转化为醛33，以准备与亚基C偶联。由炔丙醇经六步获得甲基酮形式的甲基酮55。33的醇醛缩醛反应与用（+）-DIPCl制备的55的烯醇缩醛反应，得到具有（13S）-构型的期望的β-羟基酮56，与（13R）-非对映异构体的比率为17-20：1。还原成抗二醇57并作为TIPS醚58进行选择性保护后，将C15羟基酯化得到膦酸酯59。衍生自δ-内酯60的醛62的分子内Wadsworth-Emmons反应提供了大内酯63，该大内酯63在

  DOI：

  10.1021/jo020537q

文献信息

• Total synthesis of (+)-10,10-difluorothromboxane A2 and its 9,11 and 15 stereoisomers
  作者：Stanislaw Witkowski、Y. Koteswar Rao、Ramiya H. Premchandran、Perry V. Halushka、Josef Fried

  DOI：10.1021/ja00048a017

  日期：1992.10

  An efficient total synthesis of the biologically highly active, stable (+)- 10, 10-difluorothromboxane A 2 , possessing the absolute configuration of TXA 2 , from the chiral synthon (-)-5 is described. The key intermediate, the aldehyde 25, is prepared in 16 steps with a total yield of 8.8%, which compares with 1.95% in 14 steps by our previously reported chemical-enzymatic route. Diastereoselectivity

  描述了从手性合成子 (-)-5 高效全合成具有 TXA 2 绝对构型的生物高活性、稳定 (+)- 10, 10-二氟血栓烷 A 2 。关键中间体醛 25 分 16 步制备，总产率为 8.8%，而我们之前报道的化学-酶促路线分 14 步制备的总产率为 1.95%。除了导致 13 和 14 的 Reformatsky 反应之外，所有步骤的非对映选择性都很高。 然而，两种差向异构体都已有效地转化为 25
• Diastereoface differentiation in addition of lithium enolates to chiral α,β-epoxyaldehydes
  作者：Jean-Marc Escudier、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4020(01)82375-9

  日期：1993.6

  aldolisation reaction of lithium ester enolates with chiral α,β-epoxyaldehydes 2a–2f has been investigated. The reaction proceeds with diastereofacial preference in favour of the anti isomer (anti:syn ≈ 4:1) and can be greatly enhanced in the case of cis α,β-epoxy-aldehydes 2a–2c by a synergic effect of temperature and enolate excess (anti:syn 13:1). The Felkin-Ahn model can explain the results obtained

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。
• Synthesis of Methylene-Expanded Oxetanocin Isonucleosides in Both Enantiomeric Forms¹
  作者：Michael E. Jung、Christopher J. Nichols

  DOI：10.1021/jo971890c

  日期：1998.1.1

  We report a novel route to isonucleosides of the 'methylene-expanded' oxetanocin class, in both the D-and L-enantiomeric forms, e.g., compounds L-(+)-2a, D-(-)-2a, and L-(-)-2b, beginning with the simple, known mono-p-bromobenzyl ether 3 of the very inexpensive 2-butene-1,4-diol. Sharpless asymmetric epoxidation of 3 gave either (-) or (+)-4 depending on the chirality of the tartrate used. The p-bromobenzyl ether was used since the epoxide product is crystalline and can be recrystallized to high optical purity. Opening of the epoxide with vinylmagnesium bromide gave the 1,3-diol 5, the primary alcohol of which was protected as the silyl ether 6. Treatment of 6 with iodonium bis(sym-collidine) perchlorate afforded the desired 5-(iodomethyl)tetrahydrofuran-3-ol 8 with loss of the bromobenzyl cation in the key step in the synthetic scheme. This iodide 8 was then converted into the bis(silyloxy)-protected alcohol 15 by acetylation to give the acetate 10, displacement of iodide with acetate, hydrolysis, and selective protection of the primary alcohols. The alcohol 6 could also be converted into 15 via initial acetylation and then iodocyclization to give 10. The diol 5 could also be converted into 15 by a similar route involving bis-acetylation and iodocyclization followed by functional group transformations. The tosylate of 15 was displaced with the anion of adenine or thymidine to give, alter final desilylation, the desired isonucleosides-the D-adenosine analogue (-)-2a and the L-adenosine and thymidine analogues (+)-2a and(-)-2b. All of the stereochemistry of the final products is derived from the first step of the synthesis, namely, the Sharpless asymmetric epoxidation of 3. The biological activity of the new compounds L-(+)-2a and L-(-)-2b against HIV was determined in the anti-HIV drug-testing system of the National Cancer Institute. The adenosine analogue L-(+)-2a was inactive in this screen, while the thymidine analogue L-(-)-2b showed moderate anti-HIV activity (IC50 > 2 x 10(-4) M, EC50 = 8 x 10(-7) M, TI50 > 250).
• Facile preparation of (2R,3S)- and (2S,3R)-3-[[(4-bromobenzyl)oxy]methyl]oxirane-2-methanol via asymmetric epoxidation
  作者：J. Michael Chong、Susanna Wong

  DOI：10.1021/jo00388a050

  日期：1987.6
• Synthesis of 4-C-hydroxymethyl hexopyranosyl nucleosides as potential inhibitors of HIV
  作者：Magnus Björsne、Björn Classon、ngemar Kvarnström、Bertil Samuelsson

  DOI：10.1016/s0040-4020(01)96269-6

  日期：1993.9

  The synthesis of 1-(2,3,4-trideoxy-4-C-hydroxymethyl-beta-D-erythro-hexopyranosyl)thymine (13), -uracil (15), -cytosine (16) and 9-(2,3,4-trideoxy-4-C-hydroxymethyl-beta-D-erythro-hexopyranosyl)adenine (18) are described. The nucleoside analogues were evaluated for their anti-HIV activity in vitro.