3(S)-(phenylsulfonyl)cyclohex-1-ene | 171868-69-2

• 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: 3(S)-(phenylsulfonyl)cyclohex-1-ene
• 英文别名: (S)-3-(Phenylsulfonyl)cyclohex-1-ene；(S)-3-(phenyl-sulfonyl)-cyclohexene；(S)-(cyclohex-2-en-1-ylsulfonyl)benzene；(S)-3-(Phenylsulfonyl)cyclohexene；[(1S)-cyclohex-2-en-1-yl]sulfonylbenzene
• CAS: 171868-69-2
• 化学式: C₁₂H₁₄O₂S
• 分子量: 222.308
• InChiKey: DIHRJKGTAFQMJV-GFCCVEGCSA-N

物化性质

• 沸点：
  388.7±35.0 °C(Predicted)
• 密度：
  1.188±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3(S)-(phenylsulfonyl)cyclohex-1-ene 在 四氧化锇 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 、 水 为溶剂， 以90%的产率得到2(S)-hydroxy-3(S)-(phenylsulfonyl)cyclohexan-1(S)-ol
  参考文献：
  名称：

  Asymmetric synthesis of allylic sulfones useful as asymmetric building blocks.

  摘要：

  Construction of sulfones in enantiomerically pure form provides a great opportunity to enhance their value as synthetic building blocks. Allylic sulfones, in particular, have great flexibility derived from sulfone-controlled additions to the double bond. Two strategies have been developed based upon the ability to effect asymmetric allylic alkylations with palladium employing ligands derived from c(2) symmetric diamines and 2-(diphenylphosphino)benzoic acid. Desymmetrization of meso-2-ene-1,4-diol diesters does not involve the nucleophile in the enantiodiscriminating step and thus should, a priori, not depend upon the nature of the nucleophile. Indeed, such desymmetrization of such a diester in the presence of a sulfinate anion gave excellent enantioselectivity. On the other hand, conversion of both enantiomeric allylic esters to enantiomerically pure allylic sulfones requires sodium benzenesulfinate to participate in the enantiodiscriminating step. Five-, six-, and seven-membered substrates all gave excellent enantioselectivities. A catalytic phase transfer system proved most efficacious on larger scales. propagating the asymmetry requires diastereoselective functionalization of the double bond. While epoxidation proved excellent for the five-membered ring case and satisfactory for the six-membered ring case, it was unsatisfactory in the seven-membered ring case. Osmium tetroxide-catalyzed cis-dihydroxylation gave excellent diastereoselectivities in the six- and seven-membered ring cases. Reductive cleavages produced enantiomerically pure allylic alcohols. Base-catalyzed elimination generated enantiomerically pure gamma-hydroxy-alpha,beta-unsaturated sulfones from which further stereogenic centers were produced by diastereoselective conjugate additions. Notably, an asymmetric cyclopentenone annulation using palladium-catalyzed cycloadditions now derives from racemic allyl alcohols.

  DOI：

  10.1021/ja00143a007
• 作为产物：
  描述：

  cyclohex-2-enyl methyl carbonate 、 sodium benzenesulfonate 在 bis(η3-allyl-μ-chloropalladium(II)) 、 1,2-bis[N-(2'-(diphenylphosphino)benzoyl)]-1(S),2(R)-diaminocyclohexane 、 四己基溴化铵 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以99%的产率得到3(S)-(phenylsulfonyl)cyclohex-1-ene
  参考文献：
  名称：

  Asymmetric synthesis of allylic sulfones useful as asymmetric building blocks.

  摘要：

  Construction of sulfones in enantiomerically pure form provides a great opportunity to enhance their value as synthetic building blocks. Allylic sulfones, in particular, have great flexibility derived from sulfone-controlled additions to the double bond. Two strategies have been developed based upon the ability to effect asymmetric allylic alkylations with palladium employing ligands derived from c(2) symmetric diamines and 2-(diphenylphosphino)benzoic acid. Desymmetrization of meso-2-ene-1,4-diol diesters does not involve the nucleophile in the enantiodiscriminating step and thus should, a priori, not depend upon the nature of the nucleophile. Indeed, such desymmetrization of such a diester in the presence of a sulfinate anion gave excellent enantioselectivity. On the other hand, conversion of both enantiomeric allylic esters to enantiomerically pure allylic sulfones requires sodium benzenesulfinate to participate in the enantiodiscriminating step. Five-, six-, and seven-membered substrates all gave excellent enantioselectivities. A catalytic phase transfer system proved most efficacious on larger scales. propagating the asymmetry requires diastereoselective functionalization of the double bond. While epoxidation proved excellent for the five-membered ring case and satisfactory for the six-membered ring case, it was unsatisfactory in the seven-membered ring case. Osmium tetroxide-catalyzed cis-dihydroxylation gave excellent diastereoselectivities in the six- and seven-membered ring cases. Reductive cleavages produced enantiomerically pure allylic alcohols. Base-catalyzed elimination generated enantiomerically pure gamma-hydroxy-alpha,beta-unsaturated sulfones from which further stereogenic centers were produced by diastereoselective conjugate additions. Notably, an asymmetric cyclopentenone annulation using palladium-catalyzed cycloadditions now derives from racemic allyl alcohols.

  DOI：

  10.1021/ja00143a007

文献信息

• Rapid and Stereoselective C-C, C-O, C-N and C-S Couplings via Microwave Accelerated Palladium-Catalyzed Allylic Substitutions
  作者：Ulf Bremberg、Serghey Lutsenko、Nils-Fredrik Kaiser、Mats Larhed、Anders Hallberg、Christina Moberg

  DOI：10.1055/s-2000-6298

  日期：——

  Palladium-catalyzed substitution of cyclohex-2-en-1-yl ethyl carbonate with neutral C-, O-, and N-nucleophiles was achieved in 1 - 2 minutes using microwave flash heating. Enantioselectivities up to 96% were observed. Ionic nucleophiles tended to result in lower ee. With S-nucleophiles problems with the stability of the nucleophile were encountered.

  使用微波闪热技术，在1到2分钟内实现了钯催化的环己-2-烯-1-基乙基碳酸酯与中性C-、O-和N-亲核试剂的取代反应。观察到高达96%的对映选择性。离子型亲核试剂往往导致较低的对映体过量。对于S-亲核试剂，遇到了亲核试剂稳定性问题。
• Palladium-Catalyzed Regio- and Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity
  作者：Qinglong Zhang、Dongfang Dong、Weiwei Zi

  DOI：10.1021/jacs.0c05976

  日期：2020.9.16

  widespread use in pharmaceutical chemistry. In particular, chiral allylic sulfones have drawn particular interest because of their synthetic utility. However, enantioselective synthesis of 1,3-disubstituted unsymmetrical chiral allylic sulfones remains a challenge. In this article, we report a protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- and enantioselective hydrosulfonylation of 1,3-dienes with sulfinic

  由于其在药物化学中的广泛应用，手性砜是有机合成中的重要结构基序。特别是，手性烯丙基砜因其合成效用而引起了特别的兴趣。然而，1,3-二取代的不对称手性烯丙基砜的对映选择性合成仍然是一个挑战。在本文中，我们报告了 (R)-DTBM-Segphos/Pd 催化的 1,3-二烯与亚磺酸的区域选择性和对映选择性氢磺酰化的方案，该方案提供了原子和步骤经济的 1,3-二取代手性烯丙基砜。反应条件温和，底物范围广。结合实验和计算研究表明，反应是由配体到配体的氢转移引发的，然后是通过六元过渡态的 CS 键还原消除。发现底物的烯烃 CH 与 (R)-DTBM-Segphos 的叔丁基之间的空间排斥是对映控制的关键因素。
• Highly Selective Palladium Catalyzed Kinetic Resolution and Enantioselective Substitution of Racemic Allylic Carbonates with Sulfur Nucleophiles: Asymmetric Synthesis of Allylic Sulfides, Allylic Sulfones, and Allylic Alcohols
  作者：Hans-Joachim Gais、Thomas Jagusch、Nicole Spalthoff、Frank Gerhards、Michael Frank、Gerhard Raabe

  DOI：10.1002/chem.200204657

  日期：2003.9.5

  enantioselectivity of the substitution step is, under the conditions used, independent of the chirality of the substrate; this shows that no "memory effect" is operating in this case. Hydrolysis of the carbonates ent-1 a-c, ent-3 aa and ent-3 ba, which were obtained through kinetic resolution, afforded the enantiomerically highly enriched cyclic allylic alcohols 9 a-c (>/=99 % ee) and acyclic allylic alcohols 10

  我们描述了高选择性钯催化的消旋环状烯丙基碳酸酯rac-1 ac和消旋非环状烯丙基碳酸酯rac-3aa和rac-3 ba通过与叔丁基亚磺酸盐，甲苯基亚磺酸盐，苯基亚磺酸盐阴离子和2-嘧啶硫醇反应而得到的动力学拆分。 N，N′-（1R，2R）-1，2-环己烷二基双[2-（二苯基膦基）-苯甲酰胺]（BPA）作为配体。选择性以回收的底物和产物的收率和ee值以及选择性因子S表示。在BPA存在下，碳酸环己烯酯1 a（> / = 99％ee）与2-嘧啶硫醇的反应显示出在所使用的条件下，相对于烯丙基底物的总体拟零级动力学。还描述了环状和非环状烯丙基叔丁基砜2aa，2b，2c，2d和4ac以及环状和非环状烯丙基2-嘧啶基-2-的高选择性钯催化的不对称合成。在BPA存在下，分别从相应的外消旋碳酸根，亚磺酸根阴离子和硫醇分别得到吡啶基-和4-氯苯基硫化物5aa，5b，5ab，6aa-ac，6ba和6bb。E-构
• π-Allylic Sulfonylation in Water with Amphiphilic Resin-Supported Palladium-Phosphine Complexes
  作者：Yasuhiro Uozumi、Toshimasa Suzuka

  DOI：10.1055/s-2008-1067096

  日期：——

  with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported phosphine-palladium complex in water as a single reaction medium under heterogeneous conditions to give allyl sulfones in good to high yields. Catalytic asymmetric allylic substitution of cycloalkenyl esters also took place in water using a PS-PEG resin-supported chiral imidazo-indolephosphine-palladium complex to give cycloalkenyl

  用两亲性聚苯乙烯-聚（乙二醇）（PS-PEG）树脂负载的膦-钯配合物在水中作为单一反应介质在非均相条件下进行烯丙基酯与芳基亚磺酸钠的 π-烯丙基取代，得到良好的烯丙基砜到高产。环烯基酯的催化不对称烯丙基取代也在水中使用 PS-PEG 树脂负载的手性咪唑-吲哚膦-钯络合物进行，得到高达 81% ee 的环烯基砜。
• On the Effect of a Cation Binding Site in an Asymmetric Ligand for a Catalyzed Nucleophilic Substitution Reaction
  作者：Barry M. Trost、Rumen Radinov

  DOI：10.1021/ja9706864

  日期：1997.6.1