Phenyl-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester | 412021-12-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Phenyl-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester
• 英文别名: [(3aR,5R,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl] phenylmethanesulfonate
• CAS: 412021-12-6
• 化学式: C₁₉H₂₆O₈S
• 分子量: 414.477
• InChiKey: YYLZSSDYLAPVTC-WRQOLXDDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  97.9
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Phenyl-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester 在 正丁基锂 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 64.0h， 生成 (3R,5S)-5-methyl-3-phenyl-1,2-oxathiolane 2,2-dioxide
  参考文献：
  名称：

  通过手性锂化磺酸盐的烯丙基化不对称合成α,γ-取代的γ-磺内酯

  摘要：

  描述了使用 1,2:5,6-二-O-异亚丙基-α-D-别呋喃糖作为手性助剂，通过锂化磺酸盐的 α-烯丙基化，控制对映体纯 α,γ-取代 γ-磺内酯的第一个辅助控制不对称合成。α-烯丙基化的高不对称诱导达到了良好至极好的产率。在一锅法中，磺酸中间体的辅助和非对映选择性闭环的连续无差向异构化裂解导致标题化合物的产率良好至极好以及非对映体和对映体过量（de，ee ≥ 98％）。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300342
• 作为产物：
  描述：

  1,2:5,6-二异亚丙基-alpha-D-异呋喃糖 、 苄磺酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以91%的产率得到Phenyl-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester
  参考文献：
  名称：

  Efficient asymmetric synthesis of α-alkylated benzylic methyl sulfonates

  摘要：

  The first highly efficient auxiliary-controlled synthesis of various alpha-substituted sulfortic acid derivatives is described. Alkyl or aryl halides were reacted with lithiated benzylic sulfortic esters bearing 1,2:5,6-di-O-isopropylidene-alpha-D-allofuranose as a removable enantiopure alcohol auxiliary to give the alkylated products in excellent diastereomeric excesses. The racemization-free cleavage conditions provided highly enantioenriched sulfonic acid derivatives (ee >= 98%). (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.046

文献信息

• Asymmetric Synthesis of 1,2-anti-Disubstituted Taurine Derivatives
  作者：Dieter Enders、Dirk Iffland、Gerhard Raabe

  DOI：10.1055/s-0029-1216643

  日期：2009.5

  An efficient asymmetric synthesis of anti-1,2-disubstituted taurine derivatives through nucleophilic addition of phenylmethanesulfonate to various N-acylimines in the presence of 1,2:5,6-di-O-isopropylidene-α-d-allofuranose as a chiral auxiliary is described. The taurine derivatives were obtained in three steps with good overall yields (36-61%) and excellent enantiomeric excesses (83-98%). The diastereomeric

  在1,2：5,6-二-O-异亚丙基-α - d-呋喃糖为手性存在下，通过将苯甲磺酸盐亲核加成到各种N-酰基亚胺中，有效地不对称合成抗-1,2-二取代的牛磺酸衍生物描述辅助。通过三个步骤获得了牛磺酸衍生物，其总收率良好（36-61％），对映体过量极佳（83-98％）。通过柱色谱法或重结晶可以将非对映体过量的15-91％提高到90-98％。通过X射线晶体结构分析确定产物的相对和绝对构型。 牛磺酸-不对称合成-糖助剂-N-嘧啶-α-酰胺基砜-手性助剂
• Asymmetric Synthesis of α- and α,β-Substituted β-Alkoxycarbonyl Sulfonates
  作者：Dieter Enders、Jean-Claude Adelbrecht、Wacharee Harnying

  DOI：10.1055/s-2005-872164

  日期：——

  An efficient asymmetric synthesis of substituted p-alkoxycarbonyl sulfonates is described. Enantiopure α-substituted P-alkoxycarbonyl sulfonates can be obtained via u-alkylation of metalated sulfonates bearing 1,2:5,6-di-O-isopropylidene-u-D-allofuranose as the chiral auxiliary with alkyl bromoacetates. α,β-Di-substituted P-alkoxycarbonyl sulfonates were prepared starting from the corresponding enantiopure

  描述了取代的对烷氧基羰基磺酸盐的有效不对称合成。对映体纯 α-取代的 P-烷氧基羰基磺酸盐可以通过以 1,2:5,6-二-O-异亚丙基-uD-别呋喃糖作为手性助剂的金属化磺酸盐与溴代乙酸烷基酯的 u-烷基化来获得。通过使用 TFA 裂解手性助剂并同时引起 Meyer 反应，从相应的对映纯 γ-硝基磺酸盐开始制备 α,β-二取代的 P-烷氧基羰基磺酸盐。
• Diastereo- and Enantioselective Synthesis of α,β-Disubstituted γ-Bisalkoxycarbonyl Sulfonates
  作者：Dieter Enders、Hamdollah Saeidian、Zohreh Mirjafary、Dirk Iffland、Gerhard Raabe、Jan Runsink

  DOI：10.1055/s-0029-1218017

  日期：2009.10

  The asymmetric synthesis of α,β-disubstituted γ-bisalkoxycarbonyl sulfonates is reported. The synthesis is based on the Michael addition of a lithiated enantiopure sulfonate bearing a cheap chiral sugar auxiliary to Knoevenagel acceptors. The reaction proceeds with high asymmetric inductions (ds = 69-96%) and good yields (62-79%). The absolute configuration was determined by X-ray crystal-structure analysis.

  报道了α,β-二取代γ-双烷氧羰基磺酸盐的不对称合成。该合成基于脂锂化的手性磺酸盐（含有廉价的糖类手性辅助剂）对Knoevenagel受体的Michael加成反应。反应具有高度的不对称诱导性（对映体比例为69-96%）和良好的产率（62-79%）。绝对构型通过X射线晶体结构分析确定。
• Asymmetric Michael Addition of Chiral Lithiated Sulfonates to Nitroalkenes: Diastereo- and Enantioselective Synthesis of α,β-Disubstituted γ-Nitro and β-Alkoxycarbonyl Methyl Sulfonates
  作者：Dieter Enders、Otto Berner、Nicola Vignola、Wacharee Harnying

  DOI：10.1055/s-2002-34368

  日期：——

  The diastereoselective Michael addition of lithiated enantiopure sulfonates to nitroalkenes is described. High asymmetric inductions were obtained by using 1,2:5,6-di-O-isopropylideneα-D-allofuranose as a cheap and easilyavailable chiral auxiliary. Racemization-free cleavage of the auxiliary led to α,β-disubstituted γ-nitro methyl sulfonates. A change of the cleavage conditions resulted in α,β-disubstituted

  描述了锂化的对映体纯磺酸盐与硝基烯烃的非对映选择性迈克尔加成。通过使用 1,2:5,6-二-O-异亚丙基α-D-别呋喃糖作为廉价且易于获得的手性助剂获得高度不对称诱导。助剂的无外消旋裂解产生 α,β-二取代的 γ-硝基甲基磺酸盐。裂解条件的变化通过 Meyer 反应产生 α,β-二取代的 β-烷氧基羰基磺酸盐（de ≥ 98%，ee > 98%）。
• A Practical Approach Towards the Asymmetric Synthesis of α,γ-Substituted γ-Sultones
  作者：Dieter Enders、Wacharee Harnying、Nicola Vignola

  DOI：10.1055/s-2002-34229

  日期：——

  The first auxiliary controlled synthesis of enantiopure α,γ-substituted γ-sultones via α-allylated chiral sulfonates is described. The high asymmetric inductions of the α-allylations were reached with our previously described auxiliary 1,2:5,6-di-O-isopropylidene-α-d-allofuranose (de≥98%). Cleavage of the auxiliary and successive diastereoselective ring closure of the sulfonic acid intermediates led to the title compounds in high selectivities (de, ee≥98%) and good to excellent yields (52-90%). Enantiopure α,γ-substituted γ-sultones are interesting intermediates in the reaction with various nucleophiles.

  本文描述了通过α-烯丙基化手性磺酸盐对对映纯的α,γ-取代的γ-琥珀酸内酯进行首次辅助控制合成。通过我们之前描述的辅助1,2:5,6-二-O-异亚丙基-α-d-呋喃糖（de≥98%），实现了α-烯丙基化的高不对称诱导。辅助剂的裂解和磺酸中间体的连续非对映选择性环闭合，以高选择性（de, ee≥98%）和良好至极佳的产率（52-90%）获得了标题化合物。对映纯的α,γ-取代的γ-琥珀酸内酯是与各种亲核试剂反应的有趣中间体。