(2S)-(3,3-dimethyloxiran-2-yl)methanol | 116347-29-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (2S)-(3,3-dimethyloxiran-2-yl)methanol
• 英文别名: [(2S)-3,3-dimethyloxiran-2-yl]methanol
• CAS: 116347-29-6
• 化学式: C₅H₁₀O₂
• 分子量: 102.133
• InChiKey: HJXAWVLTVYGIBH-BYPYZUCNSA-N

物化性质

• 沸点：
  58-60 °C(Press: 7 Torr)
• 密度：
  0.9912 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• 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：

  (2S)-(3,3-dimethyloxiran-2-yl)methanol 在 copper(I) bromide dimethylsulfide complex 、 二甲基硫 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (R)-3-methyl-2-vinylbutane-1,3-diol
  参考文献：
  名称：

  Stereoselective 4-Benzyloxybut-2-enylation of Aldehydes via an Allyl-Transfer Reaction Using a Chiral Allyl Donor

  摘要：

  A direct and highly stereoselective (E)-4-benzyloxybut-2-enylation of aldehydes was successfully carried out to give 5-benzyloxyhomoallylic alcohol (11) via an allyl-transfer reaction using a chiral allyl donor (10). The chiral allyl donor (10) was prepared by catalytic Sharpless asymmetric epoxidation of 3-methylbut-2-en-l-ol, followed by a stereospecific vinyl Grignard reaction of the epoxide in the presence of CuBr and selective benzylation of the primary alcohol of diol.

  DOI：

  10.1021/ol050890t
• 作为产物：
  描述：

  (S)-(3,3-dimethyloxiran-2-yl)methyl 4-nitrobenzoate 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以40%的产率得到(2S)-(3,3-dimethyloxiran-2-yl)methanol
  参考文献：
  名称：

  Synthesis of a biologically active vitamin D2 metabolite

  摘要：

  The synthesis of 1alpha,25,28-trihydroxyvitamin-D2 (1) from vitamin-D2 is described. Approaches to the upper side-chain synthon via the chiral sulfone 15, prepared either through the enzymatic resolution of 10 or the opening of the optically pure epoxide 17 with the dianion of methyl phenyl sulfone, are described. A Julia coupling of the sulfone 15 with C-1 hydroxylated aldehyde 7, obtained from vitamin-D2, gave the (22E)-isomer 24a, which was deprotected and photoisomerized to give 1.

  DOI：

  10.1021/jo00058a034

文献信息

• Total syntheses of (+)-paspalicine and (+)-paspalinine
  作者：Amos B. Smith、Toshiaki Sunazuka、Tamara L. Leenay、Jill Kingery-Wood

  DOI：10.1021/ja00178a071

  日期：1990.10

  cornerstone of the approach comprised a stereocontrolled, nine-step construction of tricyclic ketone (−)-5 [9.4% overall yield from (+)-Wieland-Miescher ketone], a prospective common intermediate containing the critical C(12b,12c) vicinal quaternary centers. In this communication we demonstrate the viability of this unified strategy with the first total syntheses of (+)-paspalicine (2) and (+)-paspalinine

  该方法的基石包括三环酮 (-)-5 的立体控制的九步构建 [(+)-Wieland-Miescher 酮的总产率为 9.4%]，这是一种含有关键 C(12b,12c) 的预期通用中间体邻近的第四纪中心。在本次交流中，我们通过 (+)-paspalinine (2) 和 (+)-paspalinine (3) 的首次全合成证明了这种统一策略的可行性
• Total synthesis of myxol and deoxymyxol stereoisomers and their application to determining the absolute configurations of the natural products
  作者：Yumiko Yamano、Miki Masumoto、Shinichi Takaichi、Akimori Wada

  DOI：10.1016/j.tet.2018.02.018

  日期：2018.3

  total synthesis of myxol stereoisomers 1a,b and deoxymyxol (plectaniaxanthin) stereoisomers 2a,b was accomplished by Wittig reaction of (S)- and (R)-C10-phosphonium salts 8a,b bearing a silyl-protected 1,2-dihydroxy-ψ end group with C30-apocarotenals 6 and 7. The phosphonium salts 8a,b were derived from aldehydes 11a,b possessing a cyclopentylidene ketal moiety, prepared via Sharpless asymmetric epoxidation

  通过带有甲硅烷基保护的1,2-的（S）-和（R）-C 10 -phosph盐8a，b的Wittig反应，完成了myxol立体异构体1a，b和deoxymyxol（plectaniaxanthin）立体异构体2a，b的总合成。具有C 30-环戊烯基6和7的二羟基-ψ端基。via盐8a，b衍生自具有环戊叉基缩酮部分的醛11a，b，其通过烯丙醇12的Sharpless不对称环氧化制备。接着是环氧乙烷环的区域选择性裂解。我们建立了使用手性柱分离立体异构体1a，b和2a，b的分析HPLC方法，从而确定了天然产物的绝对构型。HPLC分析确定了既myxol和deoxymyxol从细菌中分离具有2'小号-构型。
• Total Synthesis and Comparative Evaluation of Luzopeptin A−C and Quinoxapeptin A−C
  作者：Dale L. Boger、Mark W. Ledeboer、Masaharu Kume、Mark Searcey、Qing Jin

  DOI：10.1021/ja993019e

  日期：1999.12.1

  Full details of the total syntheses of luzopeptin A−C and quinoxapeptin A−C, C2-symmetric cyclic depsidecapeptides bearing two pendant heterocyclic chromophores, are disclosed and serve to establish the quinoxapeptin relative and absolute configuration. Key elements of the approach include the late-stage introduction of the chromophore and penultimate l-Htp acylation permitting the divergent synthesis

  公开了 luzopeptin A-C 和 quinoxapeptin A-C（带有两个侧链杂环生色团的 C2 对称环状缩肽头肽）全合成的全部细节，并用于建立 quinoxapeptin 的相对和绝对构型。该方法的关键要素包括后期引入发色团和倒数第二个 l-Htp 酰化，从而允许从常见的高级中间体合成 luzopeptins、quinoxapeptins 和结构类似物。在单个二级酰胺位点进行的 32 元环的对称五肽偶联和大环化提供了常见的环状十肽。在令人惊讶的有效无外消旋化条件下，通过在最终偶联中安装不稳定酯实现了所需五肽的会聚制备。quinoxapeptins 被证明通过高亲和力的双嵌入与 DNA 结合，类似于 Sandramycin 和 luzopeptins。显着的相似之处...
• Proton-accelerated Lewis acid catalysis for stereo- and regioselective isomerization of epoxides to allylic alcohols
  作者：Masahiro Noji、Misako Baba、Rina Hirabe、Satoshi Hayashi、Toshikatsu Takanami

  DOI：10.1039/d1cc02840e

  日期：——

  The isomerization of epoxides to allylic alcohols was developed via proton-accelerated Lewis acid catalysis. The addition of tBuOH as a proton source is the key to the efficient catalytic cycle. Trisubstituted epoxides, including enantioenriched derivatives, were selectively converted to secondary-allylic alcohols without loss of enantiopurity.

  环氧化物异构化为烯丙醇是通过质子加速的路易斯酸催化开发的。添加t BuOH 作为质子源是有效催化循环的关键。三取代的环氧化物，包括对映体富集的衍生物，在不损失对映体纯度的情况下选择性地转化为仲烯丙醇。
• Asymmetric Epoxidation of Allylic Alcohols Catalyzed by Vanadium–Binaphthylbishydroxamic Acid Complex
  作者：Masahiro Noji、Toshihiro Kobayashi、Yuria Uechi、Asami Kikuchi、Hisako Kondo、Shigeo Sugiyama、Keitaro Ishii

  DOI：10.1021/acs.joc.5b00185

  日期：2015.3.20

  acid (BBHA) complex-catalyzed asymmetric epoxidation of allylic alcohols is described. The optically active binaphthyl-based ligands BBHA 2a and 2b were synthesized from (S)-1,1′-binaphthyl-2,2′-dicarboxylic acid and N-substituted-O-trimethylsilyl (TMS)-protected hydroxylamines via a one-pot, three-step procedure. The epoxidations of 2,3,3-trisubstituted allylic alcohols using the vanadium complex of

  描述了钒-联萘基双异羟肟酸（BBHA）络合物催化的烯丙醇不对称环氧化。由（S）-1,1'-联萘-2,2'-二羧酸和N-取代-O-三甲基甲硅烷基（TMS）-保护的羟胺通过单-羟基合成旋光的基于联萘的配体BBHA 2a和2b。锅，分三步操作。使用2a的钒配合物，在TBHP水溶液中轻松地进行使用2a的钒配合物进行的2,3,3-三取代的烯丙醇的环氧化，从而得到具有良好对映选择性的优良（2 R）-环氧醇。