(4R,5R,E)-5-{[(tert-butyl)dimethylsilyl]oxy}-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-en-1-ol | 216868-39-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R,E)-5-{[(tert-butyl)dimethylsilyl]oxy}-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-en-1-ol
• 英文别名: 3-O-[(tert-butyl)(dimethyl)silyl]-1,2-dideoxy-2-[ (1E)-3-hydroxyprop-1-en-1-yl]-4,5-O-(1-methylethylidene)-D-xylitol
• CAS: 216868-39-2
• 化学式: C₁₇H₃₄O₄Si
• 分子量: 330.54
• InChiKey: RHGSBCGPGOYUEL-BETSRAJUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4R,5R,E)-5-{[(tert-butyl)dimethylsilyl]oxy}-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-en-1-ol 在 四氧化锇 、 Hydroquinone 1,4-phthalazinediyl diether 、 甲基磺酰胺 、 potassium carbonate 、 戴斯-马丁氧化剂 、 potassium hexacyanoferrate(III) 作用下， 以 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 38.0h， 生成 (E)-(4S,5S,6R,7R)-7-(tert-Butyl-dimethyl-silanyloxy)-7-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,5-dihydroxy-6-methyl-hept-2-enoic acid methyl ester
  参考文献：
  名称：

  An efficient protocol for the stereoselective dihydroxylation of ene-ester systems

  摘要：

  Dihydroxylation of ene ester systems was achieved in good yield and diastereoselectivity under classical catalytic OsO4 and NMO conditions using the intrinsic diastereoselectivity in alpha-methyl beta-OTBS systems. This intrinsic diastereoselection can be reversed using 'super' AD-mix to give the opposite diastereomer also in good selectivity. The regioselection of dihydroxylation in diene esters using a modified 'super' AD-mix was poor. This methodology can be applied towards the synthesis of part structures of the marine macrolide Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00800-x
• 作为产物：
  描述：

  tert-Butyl-[(1R,2R)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-methyl-but-3-enyloxy]-dimethyl-silane 在 二甲基硫 、 二异丁基氢化铝 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (4R,5R,E)-5-{[(tert-butyl)dimethylsilyl]oxy}-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-en-1-ol
  参考文献：
  名称：

  An efficient protocol for the stereoselective dihydroxylation of ene-ester systems

  摘要：

  Dihydroxylation of ene ester systems was achieved in good yield and diastereoselectivity under classical catalytic OsO4 and NMO conditions using the intrinsic diastereoselectivity in alpha-methyl beta-OTBS systems. This intrinsic diastereoselection can be reversed using 'super' AD-mix to give the opposite diastereomer also in good selectivity. The regioselection of dihydroxylation in diene esters using a modified 'super' AD-mix was poor. This methodology can be applied towards the synthesis of part structures of the marine macrolide Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00800-x

文献信息

• Towards Stereoselective Synthesis of the C(31)-C(39) and C(20)-C(27) Fragments of Phorboxazole A
  作者：Kammari Bal Raju、Bejjanki Naveen Kumar、Bandari Sampath Kumar、Kommu Nagaiah

  DOI：10.1002/hlca.201400279

  日期：2015.3

  The stereoselective synthesis of the C(31)–C(39) and C(20)–C(27) fragments of phorboxazole A (1) was achieved from commercially available and inexpensive D‐mannitol. Crimmins aldol reaction and a decarboxylative Claisen‐type reaction are the key steps for the C(31)–C(39) fragment, and L‐proline‐catalyzed aldol reaction, Sharpless asymmetric epoxidation, and epoxide ring opening reaction with Gilman's

  佛波唑A（1）的C（31）–C（39）和C（20）–C（27）片段的立体选择性合成是通过市售和廉价的D-甘露醇实现的。crimmins aldol反应和Claisen型脱羧反应是C（31）-C（39）片段的关键步骤，L-脯氨酸催化的aldol反应，Sharpless不对称环氧化和吉尔曼试剂的环氧化物开环反应是phorboxazole的C（20）–C（27）片段的关键步骤。