2-phenylsulfonyl-1-buten-3-ol | 133834-04-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-phenylsulfonyl-1-buten-3-ol
• 英文别名: 3-(phenylsulfonyl)but-3-en-2-ol；3-(Benzenesulfonyl)-3-buten-2-ol；3-(Benzenesulfonyl)but-3-en-2-ol
• CAS: 133834-04-5
• 化学式: C₁₀H₁₂O₃S
• 分子量: 212.269
• InChiKey: SSABBQQTYHZSBT-UHFFFAOYSA-N

物化性质

• 熔点：
  34-36 °C
• 沸点：
  404.1±37.0 °C(Predicted)
• 密度：
  1.223±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-phenylsulfonyl-1-buten-3-ol 在 jones reagent 、 zinc chloride diethyl ether 作用下， 以 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 4.0h， 生成 7,7-Dimethylbicyclo<3.1.1>heptane-2-spiro-6'-(3'-benzenesulfonyl)-2'-methyl-1'-oxahex-2'-ene
  参考文献：
  名称：

  Synthesis and reactions of .alpha.-methylene-.beta.-keto sulfones

  摘要：

  Modified Jones oxidation of 2-(benzenesulfonyl)-2-alken-1-ols and rapid nonnucleophilic workup below 0-degrees-C yields a variety of alpha-methylene-beta-keto sulfones 4, including crystalline parent 4a and also e-h, which can be stored at -20-degrees-C without change. In the absence of nucleophiles, the new compounds are stable (heating in benzene) toward dimerization and polymerization. Thus, selective cross-reactions are feasible. With alcohols, including sterically hindered tertiary alcohols and also with 2-(ethoxycarbonyl)cyclopentanone, the compounds function as efficient Micheal acceptors, even in the absence of base catalysis. In moist ether, 2-(benzenesulfonyl)-1-penten-3-one (4b) suffers rearrangement to 2-(benzenesulfonyl)ethyl propanoate (9). Sulfonylated alcohol 7 and strained alpha-hydroxyoxetane 8 are assumed as intermediates. Toward electron-rich aromatics and heteroaromatics, alpha-methylene-beta-keto sulfones 4 behave as electrophiles in Friedel-Crafts-type functionalizations. The new compounds are also dienophilic: of the two groups (acetyl and benzenesulfonyl) attached to the ethylenic terminus in 4a, benzenesulfonyl has been found to preferentially adopt the endo position in cycloadditions of cyclopentadiene and also cyclohexadiene. Prototype 3-(benzenesulfonyl)-3-buten-2-one (4a) is a crystalline methyl vinyl ketone (MVK) equivalent which, unlike MVK, undergoes controlled free-radical additions with nucleophilic radicals. In hetero-Diels-Alder reactions, 4a serves as a 1-oxa-1,3-butadiene unit, combining with a wide range of alkenes of graded nucleophilicity. Electron deficient 4a also reacts as an enophile toward 1,1-dialkylated ethylenes. In the presence of ZnCl2.OEt2, the ene reaction with beta-piene can be suppressed completely in favor of cycloaddition, giving a robustadial building block in 85% yield. In further applications to natural products chemistry, the synthesis of frontalin and novel oxatricyclics are described.

  DOI：

  10.1021/jo00013a007
• 作为产物：
  描述：

  苯基乙烯基砜 、 乙醛 在 三乙烯二胺 作用下， 生成 2-phenylsulfonyl-1-buten-3-ol
  参考文献：
  名称：

  分子内氢键控制的α-（1-羟烷基）乙烯基亚砜和砜的非对映选择性自由基加氢

  摘要：

  （S）-α-（1-羟烷基）乙烯基亚砜（S）-5与烷基和氢化三丁基锡的反应可得到高非对映选择性的加成氢化产物，而与（R）-α-（1-羟烷基）乙烯基亚砜（R）-5导致原料亚砜的完全回收。羟基和非对映体磺酰氧之间的立体选择性分子内氢键导致α-（1-羟乙基）乙烯基砜12自由基反应中的高非对映选择性。分子内氢键对非对映选择性以及对烷基的反应性具有重要作用。讨论了部首。

  DOI：

  10.1021/jo005525o

文献信息

• An easy synthesis of the 2-phenylsulfonyl-substituted allylic bromides and acetates and their reactivity towards nucleophiles
  作者：P. Auvray、P. Knochel、J.F. Normant

  DOI：10.1016/s0040-4039(00)85142-4

  日期：1986.1

  The reaction of phenyl vinyl sulfone with various aldehydes in the presence of a catalytic amount of DABCO furnishes in good yields teh corresponding 2-phenylsulfonyl-substituted alcohols which can be easily converted into their acetates or into their allylically rearranged bromides . These reagents, in turn, react with nucleophides (ketone enolates and cuprates) with an allylic rearrangement (SN2′

  在催化量的DABCO存在下，苯基乙烯基砜与各种醛的反应以良好的产率提供了相应的2-苯基磺酰基取代的醇，其可以容易地转化为其乙酸盐或烯丙基重排的溴化物。这些试剂，又与nucleophides（酮烯醇化物和铜酸盐）与烯丙基重排（S反应Ñ 2'机构），得到不饱和的官能化砜和。钯催化的反应使砜能够立体控制地转变为（Z，Z）跳过的1,4-二烯。
• Discrimination of diastereotopic sulfonyl oxygens by intramolecular hydrogen bonding: Stereoselective hydrogenation of α-sulfonyl radicals
  作者：Nobuyuki Mase、Yoshihiko Watanabe、Takeshi Toru

  DOI：10.1016/s0040-4039(99)00297-x

  日期：1999.4

  Stereoselective intramolecular hydrogen bonding between the hydroxy group and a stereogenic sulfonyl oxygen led to high diastereoselectivity in the radical reaction of α-(1-hydroxyethyl)vinyl sulfone with alkyl iodides and tributyltin hydride in the presence of triethylborane as a radical initiator. Intramolecular hydrogen bonding was demonstrated to play an important role in controlling the diastereoselectivity

  在三乙基硼烷作为自由基引发剂的存在下，α-（1-羟乙基）乙烯基砜与烷基碘化物和氢化三丁基锡的自由基反应中，羟基与立体生成的磺酰基氧之间的立体选择性分子内氢键导致高非对映选择性。分子内氢键被证明在控制非对映选择性中起重要作用。
• Contrasting pathways for the directed homogeneous hydrogenation of vinyl sulfoxides and vinyl sulfones
  作者：David Ando、Christopher Bevan、John M. Brown、David W. Price

  DOI：10.1039/c39920000592

  日期：——

  Rh-complex catalysed directed hydrogenation of (α-hydroxyalkyl)vinyl sulfones follows the same stereochemical course as the corresponding acrylates, via HO-coordination; hydrogenation of the related (α-hydroxyalkyl)vinyl sulfoxides is directed by S–O coordination, which overrides HO-participation and is shown to be general.

  Rh 络合物催化的（α-羟烷基）乙烯基砜的直接氢化反应遵循与相应丙烯酸酯相同的立体化学过程，通过 HO 配位；相关的（α-羟烷基）乙烯基亚砜的氢化是由S-O配位指导的，它优先于HO-参与，并且被证明是普遍的。
• Stereocontrol in the nucleophilic epoxidation of α-(1-hydroxyalkyl)-α,β-unsaturated sulfones
  作者：Richard F.W. Jackson、Stephen P. Standen、William Clegg、Andrew McCamley

  DOI：10.1016/s0040-4039(00)60042-4

  日期：1992.10

  Epoxidation of β-unsubstituted-α-(1-hydroxyalkyl)-α,β-unsaturated sulfones 3 with lithium t-butylperoxide proceeds with high diastereoselectivity to give the syn epoxy alcohols 6. Epoxidation of the triisopropylsilyl ethers 5, however, leads to the anti epoxy ethers 9 with moderate to good selectivity. In contrast to this, epoxidation of (E)-β-phenyl-α-(1-hydroxyalkyl)-α,β-unsaturated sulfones 4 proceeds

  β-未取代的-α-（1-羟烷基）-α，β-不饱和的砜3与叔丁基过氧化锂的环氧化以高非对映选择性进行，得到合成环氧醇6。然而，三异丙基甲硅烷基醚5的环氧化导致具有中等至良好选择性的抗环氧醚9。与此相反，（E）-β-苯基-α-（1-羟烷基）-α，β-不饱和砜4的环氧化以高非对映选择性进行，得到抗环氧醇13。相应的三异丙基甲硅烷基醚的环氧化导致非对映选择性的逆转，从而使合成环氧醚14具有适度的选择性。提出了基于1，3-烯丙基应变原理对这些结果进行合理化的方法。
• Preparation and nucleophilic substitution of (e)-1-bromo-2-phenylsulfonyl-2-alkenes and 3-acetoxy-2-phenylsulfonyl-1-alkenes
  作者：P. Auvray、P. Knochel、J.F. Normant

  DOI：10.1016/s0040-4020(01)89799-4

  日期：1988.1