Allylsulfinic acid | 154318-11-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 亚磺酸及其衍生物
• 英文名称: Allylsulfinic acid
• 英文别名: Prop-2-ene-1-sulfinic acid
• CAS: 154318-11-3
• 化学式: C₃H₆O₂S
• 分子量: 106.145
• InChiKey: UZSPFQBPERYLMS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  56.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Allylsulfinic acid 在 palladium diacetate 、 三苯基膦 作用下， 以 氘代氯仿 为溶剂， 生成 三聚丙烯
  参考文献：
  名称：

  钯催化的β，γ-不饱和甲硅烷基亚磺酸盐转化为（E）-烯烃的过程：聚丙烯酸酯片段的不对称合成

  摘要：

  在低温下，将1-烷氧基-1,3-二烯添加到路易斯或质子酸活化的二氧化硫中，生成两性离子中间体，该中间体可被环氧硅烷淬灭。可以用1：1 Pd（OAc）2 / PPh 3催化剂将所得的β，γ-不饱和甲硅烷基亚磺酸盐脱甲硅基，从而释放出相应的β，γ-不饱和亚磺酸，后者经过顺滑和高度立体选择性的逆向二氧化硫消除。该方法已应用于产生对映体纯的聚丙烯酸酯片段。

  DOI：

  10.1021/jo0357622
• 作为产物：
  描述：

  三聚丙烯 生成 Allylsulfinic acid
  参考文献：
  名称：

  SASAKI, TADAHIRO, J. AMER. CHEM. SOC., 1981, 103, 3882-3886

  摘要：

  DOI：

文献信息

• Palladium-Catalyzed Conversion of β,γ-Unsaturated Silyl Sulfinates into (<i>E</i>)-Alkenes:  Asymmetric Synthesis of Polypropionate Fragments
  作者：Xiaogen Huang、Cotinica Craita、Pierre Vogel

  DOI：10.1021/jo0357622

  日期：2004.6.1

  At low temperature, 1-alkoxy-1,3-dienes add to sulfur dioxide activated by a Lewis or protic acid generating zwitterionic intermediates that can be quenched by enoxysilanes. The resulting β,γ-unsaturated silyl sulfinates can be desilylated by 1:1 Pd(OAc)2/PPh3 catalyst, liberating the corresponding β,γ-unsaturated sulfinic acids that undergo smooth and highly stereoselective retro-ene eliminations

  在低温下，将1-烷氧基-1,3-二烯添加到路易斯或质子酸活化的二氧化硫中，生成两性离子中间体，该中间体可被环氧硅烷淬灭。可以用1：1 Pd（OAc）2 / PPh 3催化剂将所得的β，γ-不饱和甲硅烷基亚磺酸盐脱甲硅基，从而释放出相应的β，γ-不饱和亚磺酸，后者经过顺滑和高度立体选择性的逆向二氧化硫消除。该方法已应用于产生对映体纯的聚丙烯酸酯片段。
• The thermal decomposition of allylic sulfinic acids: a study of a retro-ene transition state
  作者：Steven D. Hiscock、Neil S. Isaacs、Malcolm D. King、David J. Young

  DOI：10.1039/c39940001381

  日期：——

  The thermal desulfination of allylsulfinic acid proceeds with a negative activation volume, solvent independence and a relatively small deuterium isotope effect which, together with the results of a previous stereochemical study, confirm a concerted retro-ene mechanism and suggest a relatively compact, early transition state.

  烯丙基亚磺酸的热脱硫过程具有负活化体积、独立于溶剂和相对较小的氘同位素效应，这些因素与之前的立体化学研究结果一起，证实了一种协同的逆烯机制，并提出了一种相对紧凑的早期过渡态。
• Desulfination of Allylic Sulfinic Acids: Characterization of a Retro-Ene Transition State
  作者：Stephen D. Hiscock、Neil S. Isaacs、Malcolm D. King、Rodney E. Sue、Rodney H. White、David J. Young

  DOI：10.1021/jo00127a022

  日期：1995.11

  Allylic sulfinic acids have been prepared by cleavage of trialkyltin allylic sulfinates with trifluoroacetic acid (TFA). Allylsulfinic acid prepared in this way could be trapped as the sodium salt or observed by NMR and UV spectroscopy to undergo spontaneous decomposition to propene and sulfur dioxide at ambient temperatures. The corresponding reaction of 1-methylprop-2-enylsulfinic acid was regiospecific, yielding (E)- and (Z)-2-butene (E:Z = 82:18). Acidolysis of E/Z mixtures of trimethyltin 5-methylcyclohex-2-enylsulfinate with [H-2]-TFA followed by desulfination indicated that the latter process proceeded with gamma-syn deuterium migration, consistent with a concerted, retro-ene mechanism. A detailed kinetic investigation of allylsulfinic acid desulfination supported this conclusion. This reaction obeyed a first order rate law (k(297K) = (5.5 +/- 0.1) x 10(-4) s(-1) in toluene) with a large, negative activation entropy (Delta S double dagger = -146 +/- 17 J K-1). The rate of desulfination was essentially independent of solvent. The volume profile (Delta V double dagger = -5.5 +/- 1.0 cm(3) mol(-1), Delta V = 15 +/- 5 cm(3) mol(-1)) is comparable to that of a retro Diels-Alder reaction and taken together with the above evidence and a relatively small deuterium kinetic isotope effect (k(H)/k(D) = 2.5 +/- 0.1) strongly supports a concerted desulfination, proceeding via a relatively compact, early transition state.
• SASAKI, TADAHIRO, J. AMER. CHEM. SOC., 1981, 103, 3882-3886
  作者：SASAKI, TADAHIRO

  DOI：——

  日期：——
• Desulfinylation of Prop-2-enesulfinic Acid: Experimental Results and Mechanistic Theoretical Analysis
  作者：Adrián Varela-Álvarez、Dean Marković、Pierre Vogel、José Ángel Sordo

  DOI：10.1021/ja901565s

  日期：2009.7.15

  dimer (13)(2). SO(2), CF(3)COOH, and BF(3) x Me(2)O do not catalyze the reaction. In the presence of an excess of BF(3) x Me(2)O the desulfinylation is completely inhibited due to the formation of a stable tetramolecular complex of type (CH(2)=CHCH(2)SO(2)H x BF(3))(2) (18), for which quantum calculations show that the S=O/sigma(C(1)-C(2)) bonds are antiperiplanar whereas the S-OH/sigma(C(1)-C(2)) bonds

  在-15 摄氏度的 CH(2)Cl(2) 溶液中丙-2-烯亚磺酸 (13) 脱亚磺酰化的势能面已经通过量子计算进行了探索，并用在不存在或不存在的情况下获得的反应动力学数据进行了分析。添加剂的存在。单体 13 采用优选构象，gauche S=O/sigma(C(1)-C(2) 键对和 OH 键指向 C(3)。它与更稳定的二聚体 (13)(2) 平衡（在 -15 摄氏度）由两个 OH...O=S 氢键形成，其中 S=O/sigmaC(1)-C(2) 也是 gauche，但 SOH 部分相对于 sigma( C(1)-C(2)。二聚体 (13)(2) 经历脱硫酰化成丙烯 + SO(2) + 13 遵循一步协调机制。首选的过渡态是六元椅子状过渡结构（C...S 伸长率和 SO...H... C(3) 氢转移同时发生)，其中 S=O/sigma(C(1)-C(2)) 键是 gauche（S=O 采用伪轴位置）。至少有