trans-6-oxabicyclo<3.1.0>hexan-2-ol | 34310-95-7

• 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: trans-6-oxabicyclo<3.1.0>hexan-2-ol
• 英文别名: trans-2,3-Epoxycyclopentanol；2,3-epoxycyclopentanol；trans-6-oxabicyclo[3.1.0]hexan-2-ol；(1S,2R,5R)-6-oxabicyclo[3.1.0]hexan-2-ol
• CAS: 34310-95-7
• 化学式: C₅H₈O₂
• 分子量: 100.117
• InChiKey: NEMITCBDWZCQGL-WDCZJNDASA-N

物化性质

• 沸点：
  229.4±8.0 °C(Predicted)
• 密度：
  1.326±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-6-oxabicyclo<3.1.0>hexan-2-ol 在 palladium on activated charcoal 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 氢氧化钾 、 phosphate buffer 、 pig liver esterase 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 四氢呋喃 、 乙醇 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 20.0~95.0 ℃ 、1.01 MPa 条件下， 反应 49.0h， 生成 N-[2-hydroxy-5-(9-phenylxanthen-9-yloxy)cyclopentyl]-2-(thymin-1-yl)acetamide
  参考文献：
  名称：

  Synthesis of Cyclopentane Amide DNA (cpa-DNA) and Its Pairing Properties

  摘要：

  We recently reported on the synthesis and pairing properties of the DNA analogue bicyclo[3.2.1]-amide DNA (bca-DNA). In this analogue the nucleobases are attached via a linear, 4-bond amide-linker to a structurally preorganized sugar-phosphate backbone unit. To define the importance of the degree of structural rigidity of the bca-backbone unit on the pairing properties, we designed the structurally simpler cyclopentane amide DNA (cpa-DNA), in which the bicyclo[3.2.1]-scaffold was reduced to a cyclopentane unit while the base-linker was left unchanged. Here we present a synthetic route to the enantiomerically pure cpa-DNA monomers and the corresponding phosphoramidites containing the bases A and T, starting from a known, achiral precursor in 9 and 12 steps, respectively. Fully modified oligodeoxynucleotides were synthesized by standard solid-phase oligonucleotide chemistry, and their base-pairing properties with complementary oligonucleotides of the DNA-, RNA-, bca-DNA-, and cpa-DNA-backbones were assessed by UV melting curves and CD-spectroscopic methods. We found that cpa-oligoadenylates form duplexes with complementary DNA that are less stable by -2.7 degreesC/mod. compared to DNA. The corresponding cpa-oligothymidylates do not participate in complementary base-pairing with any of the investigated backbone systems except with its own (homo-duplex). As its congener bca-DNA, cpa-DNA seems to prefer left-handed helical duplex structures with DNA or with itself as indicated by the CD spectra.

  DOI：

  10.1021/jo034143q
• 作为产物：
  描述：

  (2-环戊烯-1-氧基)二甲基(1,1-二甲基乙基)硅烷 在 四丁基氟化铵 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 trans-6-oxabicyclo<3.1.0>hexan-2-ol
  参考文献：
  名称：

  Synthesis of Cyclopentane Amide DNA (cpa-DNA) and Its Pairing Properties

  摘要：

  We recently reported on the synthesis and pairing properties of the DNA analogue bicyclo[3.2.1]-amide DNA (bca-DNA). In this analogue the nucleobases are attached via a linear, 4-bond amide-linker to a structurally preorganized sugar-phosphate backbone unit. To define the importance of the degree of structural rigidity of the bca-backbone unit on the pairing properties, we designed the structurally simpler cyclopentane amide DNA (cpa-DNA), in which the bicyclo[3.2.1]-scaffold was reduced to a cyclopentane unit while the base-linker was left unchanged. Here we present a synthetic route to the enantiomerically pure cpa-DNA monomers and the corresponding phosphoramidites containing the bases A and T, starting from a known, achiral precursor in 9 and 12 steps, respectively. Fully modified oligodeoxynucleotides were synthesized by standard solid-phase oligonucleotide chemistry, and their base-pairing properties with complementary oligonucleotides of the DNA-, RNA-, bca-DNA-, and cpa-DNA-backbones were assessed by UV melting curves and CD-spectroscopic methods. We found that cpa-oligoadenylates form duplexes with complementary DNA that are less stable by -2.7 degreesC/mod. compared to DNA. The corresponding cpa-oligothymidylates do not participate in complementary base-pairing with any of the investigated backbone systems except with its own (homo-duplex). As its congener bca-DNA, cpa-DNA seems to prefer left-handed helical duplex structures with DNA or with itself as indicated by the CD spectra.

  DOI：

  10.1021/jo034143q

文献信息

• Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)
  作者：Waldemar Adam、Catherine M. Mitchell、Chantu R. Saha‐Möller

  DOI：10.1002/(sici)1099-0690(199904)1999:4<785::aid-ejoc785>3.0.co;2-#

  日期：1999.4

  Good cis selectivity is observed in the epoxidation of the cyclic allylic alcohols 2-cyclopentenol and 2-cyclohexenol due to a hydroxy-directing effect through hydrogen bonding; however, for 2-cycloheptenol and 2-cyclooctenol hydrogen bonding is ineffective and steric interactions cause a higher trans selectivity. The conformationally fixed cis- and trans-5-tert-butyl-2-cyclohexenols serve as suitable

  对于一系列的3-烷基取代的环己烯，已经评估了在用甲基三氧or /脲/过氧化氢加合物（MTO / UHP）进行环氧化时，烯丙基取代基的空间效应。的反式与取代基的大小选择性增加，并且非对映选择性遵循塔夫脱（的立体取代基常数的良好的线性相关性ë小号）或Charton（ν）。由于通过氢键的羟基引导作用，在环状烯丙基醇2-环戊烯醇和2-环己烯醇的环氧化中观察到良好的顺式选择性。但是，对于2-环庚烯醇和2-环辛烯醇，氢键无效，空间相互作用会导致更高的反式选择性。构象固定的顺式和反式-5-叔丁基-2-环己烯醇用作合适的底物，用于测量在这些环氧化反应中的氧转移的过渡态的二面角。因此，MTO / UHP氧化剂有利于一个准赤道有效氢键（羟基-组指向性）的羟基的结构，以类似于米氯过苯甲酸（米-CPBA）和二甲基二（DMD），和一个二面角约。建议130°。
• A Highly Chemoselective, Diastereoselective, and Regioselective Epoxidation of Chiral Allylic Alcohols with Hydrogen Peroxide, Catalyzed by Sandwich-Type Polyoxometalates:  Enhancement of Reactivity and Control of Selectivity by the Hydroxy Group through Metal−Alcoholate Bonding
  作者：Waldemar Adam、Paul L. Alsters、Ronny Neumann、Chantu R. Saha-Möller、Dorit Sloboda-Rozner、Rui Zhang

  DOI：10.1021/jo0266386

  日期：2003.3.1

  Sandwich-type polyoxometalates (POMs), namely [WZnM2(ZnW9O34)2]q- [M = Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], are shown to catalyze selectively the epoxidation of chiral allylic alcohols with 30% hydrogen peroxide under mild conditions (ca. 20 degrees C) in an aqueous/organic biphasic system. The transition metals M in the central ring of polyoxometalate do not affect the reactivity

  三明治型多金属氧酸盐（POM），即[WZnM2（ZnW9O34）2] q- [M = Mn（II），Ru（III），Fe（III），Pd（II），Pt（II），Zn（II） ; q = 10-12]，表明在温和条件下（约20摄氏度）在水/有机双相体系中，用30％过氧化氢选择性催化手性烯丙醇的环氧化。多金属氧酸盐中心环中的过渡金属M不影响过氧化氢使烯丙醇环氧化的反应性，化学选择性或立体选择性。对于空洞的Keggin POM [PW11O39] 7-，可以观察到相似的选择性，尽管产物收率明显降低，其中过氧钨酸盐络合物已被证明是活性氧化物质。所有这些特征都支持钨过氧配合物，而不是高价过渡金属氧物种作为三明治型POM催化环氧化的关键中间体。通过乙酰化或甲基化将羟基官能团封端时，这些POM未观察到这些羟基保护的底物[1a（Ac）和1a（Me）]的反应性。提出了一种模板来说明反应性和选择性的显着提高，
• Hydroxy-assisted chemo- and stereo-selective epoxidation catalysed by a titanium silicate molecular sieve (TS-1)/H2O2 system
  作者：Rajiv Kumar、Godwin C. G. Pais、Bipin Pandey、Pradeep Kumar

  DOI：10.1039/c39950001315

  日期：——

  The TS-1/H2O2 system efficiently catalyses the hydroxy-assisted chemoselective epoxidation of α-hydroxyalkene in geraniol, and the stereoselective epoxidation of cyclopent-2-en-1-ol/cyclohex-2-en-1-ol producing the epoxide which is cis to OH with high selectivity (90:10 cis: trans).

  TS-1/H2O2 系统能高效催化香叶醇中 α-羟基烯的羟基辅助化学选择性环氧化反应，以及环戊-2-烯-1-醇/环己-2-烯-1-醇的立体选择性环氧化反应，产生的环氧化物具有高选择性（90:10 顺：反），即顺式为羟基。
• Chemo- and diastereoselectivities in the oxidation of cyclopentenols with dimethyldioxirane and methyl(trifluoromethyl)dioxirane
  作者：Lucia D'Accolti、Michele Fiorentino、Caterina Fusco、Angela M. Rosa、Ruggero Curci

  DOI：10.1016/s0040-4039(99)01607-x

  日期：1999.11

  diastereoselectivity and the chemoselectivity (epoxidation versus allylic oxidation) attained in the oxidation of cyclopentenols using dimethyldioxirane and methyl(trifluoromethyl)dioxirane is reported. The results indicate that with both dioxiranes diastereoselective epoxidation of allylic cyclopentenols is accompanied by competitive allylic oxidation to the corresponding enone; for the latter, a likely

  报道了使用二甲基二环氧乙烷和甲基（三氟甲基）二环氧乙烷在环戊烯醇的氧化中获得的非对映选择性和化学选择性（环氧化与烯丙基氧化）的比较。结果表明，对于两种二恶英，烯丙基环戊烯醇的非对映选择性环氧化都伴随着竞争性烯丙基氧化成相应的烯酮。对于后者，提出了可能的理由。
• Synthesis and Ring-Opening Reactions of the Diastereoisomericcis- andtrans-Epoxides Derived from 3-(Benzyloxy)cyclopentene and 2-(Benzyloxy)-2,5-dihydrofuran
  作者：Paolo Crotti、Valeria Di Bussolo、Lucilla Favero、Franco Macchia、Mauro Pineschi

  DOI：10.1002/(sici)1099-0690(199808)1998:8<1675::aid-ejoc1675>3.0.co;2-b

  日期：1998.8