(+/-)-1,1'-Methylenedi[(1RS,1'RS,5SR,5'SR)-3-oxo-8-oxabicyclo[3.2.1]oct-6-ene]

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+/-)-1,1'-Methylenedi[(1RS,1'RS,5SR,5'SR)-3-oxo-8-oxabicyclo[3.2.1]oct-6-ene]
• 英文别名: 1,1'-methylenedi[(1RS,1'SR,5SR,5'RS)-3-oxo-8-oxabicyclo[3.2.1]oct-6-en-1-yl]；1,1'-methylenedi[(1RS,1'SR,5SR,5'RS)-8-oxabicyclo[3.2.1]oct-6-en-3-one]；(1S,5R)-1-[[(1S,5R)-3-oxo-8-oxabicyclo[3.2.1]oct-6-en-1-yl]methyl]-8-oxabicyclo[3.2.1]oct-6-en-3-one
• 化学式: C₁₅H₁₆O₄
• 分子量: 260.29
• InChiKey: BMSMGXQHHRZWFU-BYNSBNAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-1,1'-Methylenedi[(1RS,1'RS,5SR,5'SR)-3-oxo-8-oxabicyclo[3.2.1]oct-6-ene] 在 potassium tri-sec-butyl-borohydride 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到(-)-1,1'-methylenedi[(1R,1'R,3R,3'R,5R,5'R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol]
  参考文献：
  名称：

  Synthesis of 1,1′-methylenedi[(1 R ,1′ R ,3 R ,3′ R ,5 R ,5′ R )-8-oxabicyclo[3.2.1]oct-6-en-3-ol] and derivatives: precursors of long-chain polyketides

  摘要：

  Racemic 1,1'-methylene[(1RS, 1'RS, 3RS, 3'RS, 5RS, 5'RS)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] ((+/-)-6) derived from 2,2'-methylenedifuran has been resolved kinetically with Candida cylindracea lipase-catalysed transesterification giving 1,1'-methylenedi[(1R, 1'R, 3R, 3'R, 5R, 5'R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] (-)-6 (30% yield, 98% ee) and 1,1'-methylenedi[(1S, 1'S, 3S, 3'S, 5S, 5'S)-8-oxabicyclo[3.2.1]oct-6-en-3-yl] diacetate (+)-8, (40% yield, 98% ee). These compounds have been converted into 1,1'-methylenedi[(4S, 4'S, 6S, 6'S)- and (4R, 4'R, 6R, 6'R)-cyclohept-1-en-4,6-diyl] derivatives. (C) 2001 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(00)00475-4
• 作为产物：
  描述：

  2-(呋喃-2-基甲基)呋喃 、 1,1,3,3-四氯丙酮 在 六氟异丙醇 、 三乙胺 、 铜 、 氯化铵 、 锌 作用下， 以 甲醇 为溶剂， 反应 120.0h， 以55%的产率得到meso-1,1'-methylenedi[(1R,1'S,5S,5'R)-3-oxo-8-oxabicyclo[3.2.1]oct-6-en-1-yl]
  参考文献：
  名称：

  长链1,3-多元醇的新的非迭代不对称合成。

  摘要：

  提出了一种新的不对称合成pentadeca-1,3,5,7,9,11,13,15-辛醇及其衍生物的方法。它基于4,4'-亚甲基[（1R，1'S，6R，6'S）-6-乙酰氧基环庚-3-烯-1-基]双（4-甲氧基苯甲酸酯）的Sharpless不对称二羟基化（AD）（9）衍生自1,1,3-三氯-2-氧基烯丙基阳离子与2,2'-亚甲基二呋喃（1）的双[3 + 4]环加成。以“ AD-mix-beta（5x）”从9中以98.4％ee获得的二醇（-）-10被氧化成（2R和2S，4S，6R）-四氢-2-羟基-6-（（4S ，6S）-（6-羟基-4-[（4-甲氧基苯甲酰基）氧基]环庚-1-烯-1-基）-2-氧丙基）-2H-吡喃-4-基4-甲氧基苯甲酸酯（（-）- 18）。通过结合Evans的anti和Nasaraka的aldol（-）-18顺式还原与双重Mitsunobu反应，形成16个非对映异构体pentadeca-1

  DOI：

  10.1002/1521-3765(20001117)6:22<4091::aid-chem4091>3.0.co;2-w

文献信息

• Scope and Limitations of the Double [4+3]-Cycloadditions of 2-Oxyallyl Cations to 2,2‘-Methylenedifuran and Derivatives
  作者：Kai Torsten Meilert、Marc-Etienne Schwenter、Yuli Shatz、Srinivas Reddy Dubbaka、Pierre Vogel

  DOI：10.1021/jo020678s

  日期：2003.4.1

  The reactivity of various 2-oxyallyl cations toward 2,2'-methylenedifuran (1b), 2,2'-(hydroxymethyl)difuran (1c), 2,2'-(trimethylsilylmethylene)difuran (1d), and di(2-furyl)methanone (1e) has been explored. Difuryl derivatives 1c, 1d, and le refused to undergo formal double [4+3]-cycloadditions. Conditions have been found to convert 1b into meso-1,1'-methylenedi[(1R,1'S,5S,5'R)- (3) and (+/-)-1,1'- methylenedi[(1RS, 1'SR,5SR,5'RS)-8-oxabicyclo[3.2.1]oct-6-en-3-one] (4) that do not require CF3CH(OH)CF3 as solvent. High yields of meso-1,1'-methylenedi[(1R,1'S,2S,2'R,4R,4'S,5S,5'R)- (5) and (+/-)-1,1'-methylenedi[(1RS,1'RS,2SR,2'SR,4RS,4'RS,5SR,5'SR)-2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6- en-3-one] (6) have been obtained when 1b was reacted with 2,4-dibromopentan-3-one (7h) and NaI/Cu.
• A New, Non-Iterative Asymmetric Synthesis of Long-Chain 1,3-Polyols
  作者：Marc-Etienne Schwenter、Pierre Vogel

  DOI：10.1002/1521-3765(20001117)6:22<4091::aid-chem4091>3.0.co;2-w

  日期：2000.11.17

  A new approach to the asymmetric synthesis of pentadeca-1,3,5,7,9,11,13,15-octols and their derivatives is presented. It is based on the Sharpless asymmetric dihydroxylation (AD) of 4,4'-methylene[(1R,1'S,6R,6'S)-6-acetoxycyclohept-3-en-1-yl]bis(4-methoxybenzoate) (9), derived from a double [3+4] cycloaddition of the 1,1,3-trichloro-2-oxyallyl cation with 2,2'-methylenedifuran (1). The diol (-)-10

  提出了一种新的不对称合成pentadeca-1,3,5,7,9,11,13,15-辛醇及其衍生物的方法。它基于4,4'-亚甲基[（1R，1'S，6R，6'S）-6-乙酰氧基环庚-3-烯-1-基]双（4-甲氧基苯甲酸酯）的Sharpless不对称二羟基化（AD）（9）衍生自1,1,3-三氯-2-氧基烯丙基阳离子与2,2'-亚甲基二呋喃（1）的双[3 + 4]环加成。以“ AD-mix-beta（5x）”从9中以98.4％ee获得的二醇（-）-10被氧化成（2R和2S，4S，6R）-四氢-2-羟基-6-（（4S ，6S）-（6-羟基-4-[（4-甲氧基苯甲酰基）氧基]环庚-1-烯-1-基）-2-氧丙基）-2H-吡喃-4-基4-甲氧基苯甲酸酯（（-）- 18）。通过结合Evans的anti和Nasaraka的aldol（-）-18顺式还原与双重Mitsunobu反应，形成16个非对映异构体pentadeca-1
• Synthesis of 1,1′-methylenedi[(1 R ,1′ R ,3 R ,3′ R ,5 R ,5′ R )-8-oxabicyclo[3.2.1]oct-6-en-3-ol] and derivatives: precursors of long-chain polyketides
  作者：Aurelio G. Csákÿ、Pierre Vogel

  DOI：10.1016/s0957-4166(00)00475-4

  日期：2000.12

  Racemic 1,1'-methylene[(1RS, 1'RS, 3RS, 3'RS, 5RS, 5'RS)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] ((+/-)-6) derived from 2,2'-methylenedifuran has been resolved kinetically with Candida cylindracea lipase-catalysed transesterification giving 1,1'-methylenedi[(1R, 1'R, 3R, 3'R, 5R, 5'R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] (-)-6 (30% yield, 98% ee) and 1,1'-methylenedi[(1S, 1'S, 3S, 3'S, 5S, 5'S)-8-oxabicyclo[3.2.1]oct-6-en-3-yl] diacetate (+)-8, (40% yield, 98% ee). These compounds have been converted into 1,1'-methylenedi[(4S, 4'S, 6S, 6'S)- and (4R, 4'R, 6R, 6'R)-cyclohept-1-en-4,6-diyl] derivatives. (C) 2001 Published by Elsevier Science Ltd.