(Z)-2,3-bis(hydroxymethyl)-1-methylenecyclopropane | 57476-07-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2,3-bis(hydroxymethyl)-1-methylenecyclopropane
• 英文别名: [2-(hydroxymethyl)-3-methylenecyclopropyl]methanol；cis-2,3-bis(hydroxymethyl)methylenecyclopropane；cis-Feist's Diol；[(1R,2S)-3-Methylidenecyclopropane-1,2-diyl]dimethanol；[(1R,2S)-2-(hydroxymethyl)-3-methylidenecyclopropyl]methanol
• CAS: 57476-07-0；57637-10-2；139891-19-3；57476-08-1
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: SUAJNHGXHTVCFN-OLQVQODUSA-N

物化性质

• 沸点：
  200.7±25.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-2,3-bis(hydroxymethyl)-1-methylenecyclopropane 在 Jones reagent 、 lipase AK 作用下， 以 异丙醚 、 丙酮 为溶剂， 反应 2.0h， 生成 (-)-(1S,2R)-2-(acetoxymethyl)-3-methylenecyclopropanecarboxylic Acid
  参考文献：
  名称：

  核苷亚甲基环丙烷类似物的合成及生物评价

  摘要：

  摘要 从手性亚甲基环丙烷结构单元开始，该结构单元是通过内消旋二醇的酶促脱对称反应容易获得的，合成了两种类型的核苷亚甲基环丙烷类似物。第一类核苷是通过在Mitsunobu反应条件下将手性结构单元与6-氯嘌呤直接偶联，然后将嘌呤碱官能化而获得的。第二种核苷以库尔修斯重排为关键步骤，然后通过线性方法构建尿嘧啶杂环。这些衍生物被评估为对抗重要病毒病原体的潜在药物。新化合物在100μg/ mL的浓度下均无明显的抗病毒活性，这是测试的最高浓度。 从手性亚甲基环丙烷结构单元开始，该结构单元是通过内消旋二醇的酶促脱对称反应容易获得的，合成了两种类型的核苷亚甲基环丙烷类似物。第一类核苷是通过在Mitsunobu反应条件下将手性结构单元与6-氯嘌呤直接偶联，然后将嘌呤碱官能化而获得的。第二种核苷以库尔修斯重排为关键步骤，然后通过线性方法构建尿嘧啶杂环。这些衍生物被评估为对抗重要病毒病原体的潜在药物。新化合物在100μg/

  DOI：

  10.1055/s-0033-1339311
• 作为产物：
  描述：

  6-Methylene-3-oxa-bicyclo[3.1.0]hexane-2,4-dione 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (Z)-2,3-bis(hydroxymethyl)-1-methylenecyclopropane
  参考文献：
  名称：

  Hydrocarbon thermal degenerate rearrangements. IV. Stereochemistry of the methylenecyclopropane self-interconversion. Chiral and achiral intermediates

  摘要：

  DOI：

  10.1021/ja00747a019

文献信息

• Nickel-Catalyzed Regio- and Stereoselective Reductive Coupling between Methylenecyclopropanes, Aldehydes, and Triethylborane with Retention of the Cyclopropane Ring
  作者：Kenichi Ogata、Daisuke Shimada、Shin-ichi Fukuzawa

  DOI：10.1002/chem.201200271

  日期：2012.5.14

  Running rings: The first regio‐ and stereoselective reductive coupling between methylenecyclopropanes, aldehydes, and triethylborane with retention of the cyclopropane ring was achieved using a nickel–phosphine catalyst (see scheme). The reductive coupling reaction constructed a stereo‐defined cyclopropane ring with formation of a quaternary stereogenic carbon center.

  运转环：使用镍-膦催化剂（见方案）在亚甲基环丙烷，醛和三乙基硼烷之间保留环丙烷环的第一区域和立体选择性还原偶联。还原偶联反应构建了一个立体定义的环丙烷环，并形成了一个四级立体原子碳中心。
• Preparation of both enantiomers of a synthon for novel nucleoside analogs by enzymatic desymmetrization of a meso-diol with a methylene cyclopropane skeleton
  作者：Germain Obame、Hélène Pellissier、Nicolas Vanthuyne、Jean-Bernard Bongui、Gérard Audran

  DOI：10.1016/j.tetlet.2010.12.097

  日期：2011.3

  The enzymatic desymmetrization of methylenecyclopropane diol or its corresponding diacetate derivative, generated from a [2+1] cycloaddition between dioxepin and methylchlorocarbene, is described. After screening five commercial lipases, the two enantiomers of acetic acid 2-hydroxymethyl-3-methylene-cyclopropylmethyl ester are obtained in high yields and excellent enantioselectivities by using PFL

  描述了亚甲基环丙烷二醇或其相应的二乙酸酯衍生物的酶促脱对称，该二甲基环氧丙烷是由二氧杂环庚烷和甲基氯卡宾之间的[2 + 1]环加成反应生成的。在筛选出五种商业脂肪酶后，通过在有机溶剂中使用PFL或LPP，可以高收率和优异的对映选择性获得乙酸2-羟基甲基-3-亚甲基-环丙基甲基酯的两种对映体。通过X射线分析建立了去对称产物的立体结构。我们还报道了这种非外消旋手性结构单元的新例子，其中旋光的迹象显着取决于溶剂并被反转。使用这些对映体纯的组成部分，还提出了新型核苷类似物的合成。
• Reactions of co-ordinated ligands. Part XIII. Ring opening of 2,3-bis-(hydroxymethyl)methylenecyclopropane with nonacarbonyldi-iron: molecular and crystal structures of tricarbonyl-η⁴-[3-methylene-endo-4-vinyldihydrofuran-2(3H)-one]iron(<scp>0</scp>) and tetracarbonyl-η²-[3-methyl-ene-exo-4-vinyldihydrofuran-2(3H)-one]iron(<scp>0</scp>)
  作者：Barbara M. Chisnall、Michael Green、Russell P. Hughes、Alan J. Welch

  DOI：10.1039/dt9760001899

  日期：——

  trans- or cis-2,3-Bis(hydroxymethyl)methylenecyclopropanes react with [Fe2(CO)9] to produce tricarbonyl-η4-[3-methylene-endo-4-vinyldihydrofuran-2(3H)-one]iron(0) and tetracarbonyl-η2-[3-methylene-exo-4-vinyldihydro-furan-2(3H)-one]iron(0). The structural identities of these two complexes have been established by the analysis of single-crystal X-ray data recorded on a four-circle diffractometer.

  反式-或顺式-2,3-双（羟甲基）亚甲基环带的[Fe反应2（CO）9 ]以产生三羰基-η 4 - [3-亚甲基-内-4- vinyldihydrofuran-2（3 ħ） -酮]铁（0）和四羰-η 2 - [3-亚甲基-外-4- vinyldihydro -呋喃-2-（3 ħ） -酮]铁（0）。通过分析记录在四圆衍射仪上的单晶X射线数据，已经确定了这两种络合物的结构特征。
• Synthesis of (<i>Z</i>)-(2,3-bis-Hydroxymethyl)methylenecyclopropane Analogues of Purine Nucleosides
  作者：Xinchao Chen、Shintaro Matsumi、Hiroaki Mitsuya、Jiri Zemlicka

  DOI：10.1081/ncn-120021426

  日期：2003.6

  Synthesis of (Z)-(2,3-bis-hydroxymethyl)methylenecyclopropane analogues of nucleosides adenosine 10a, 10b, 10c and 17 is described. Epimerization of Feist's acid (11) using acetic anhydride gave cyclic anhydride 12 which was reduced in situ to give diol 13. Acetylation (compound 14) followed by addition of bromine led to dibromo derivative 15. Alkylation-elimination of adenine with 15 afforded, after deacetylation, analogue 10a. Similar treatment of 2-amino-6-chloropurine and 2,6-diaminopurine led to diacetates 16 and 18. Deprotection then gave compounds 17 and 10c. Hydrolysis of 17 furnished guanine analogue 10b. Compounds 10a, l0b or 10c were inactive against HCMV, HSV-1, HSV-2, EBV, VZV and HBV. Analogues 10a and 10b were also assayed for anti-HIV activity. Compound 10a was effective in HIV-1/MT-2 culture with EC50/CC50 33/> 100 muM but 10b was inactive. Analogue 10a was not a substrate for adenosine deaminase.
• Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Yuto Akai、Takeshi Yamamoto、Yuuya Nagata、Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/ja303506k

  日期：2012.7.11

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.