3,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene | 596127-54-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 3,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene
• 英文别名: (+)-(R,R,R,R)-UlluPHOS；3,4-bis[(2R,5R)-2,5-dimethylphospholan-1-yl]-2,5-dimethylthiophene
• CAS: 596127-54-7
• 化学式: C₁₈H₃₀P₂S
• 分子量: 340.45
• InChiKey: QDESAQCWGHWXJF-AAVRWANBSA-N

物化性质

• 沸点：
  452.7±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 3,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  通过对映体选择性加氢催化以高对映体纯度合成完全相同的（-）-（S，S）-7-羟基cal醛的工艺规模

  摘要：

  与自然界相同的（-）-（S，S）-7-羟基cal胺（=（-）-（5 S，8 S）-5,6,7,8-四氢-3-羟基借助手性Ru配合物，开发了96％对映异构体过量（ee）的-5-甲基-8-（1-甲基乙基）萘-2-甲醛；（-）- 1a）。关键步骤是将易于获得的2-（4-甲氧基苯基）-3-甲基丁-2-烯酸（10）在86％ee中对映体选择性氢化为（+）- 11（方案5和表1）。通过诱导中间体（+）-3,4-二氢-4-（1-甲基乙基）-7-甲氧基-2的结晶，光学纯度（96％ee）大大提高。H-萘-1-酮（（+）- 3）。对类似物（-）- 9进行的计算构象分析合理化了CC键催化加氢中获得的高非对映选择性。

  DOI：

  10.1002/hlca.200590139
• 作为产物：
  描述：

  2,5-dimethyl-3,4-diiodo-thiophene 在 palladium diacetate lithium aluminium tetrahydride 、 正丁基锂 、 三甲基氯硅烷 作用下， 以 四氢呋喃 为溶剂， 反应 29.5h， 生成 3,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene
  参考文献：
  名称：

  2,5-Dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene:  First Member of the Hetero-DuPHOS Family

  摘要：

  The 2,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholanolthiophene (UluPHOS), a new thiophene-based analogue of (RR)-1,2-bis(phospholano)benzene (Me-DuPHOS), was synthesized, geometrically and electronically characterized, and employed as ligand of Rh and Ru in some standard hydrogenation reactions of prostereogenic functionalized carbon-carbon and carbon-oxygen double bonds. The synthesis of UlluPHOS is much easier than that provided for Me-DuPHOS. UlluPHOS and Me-DuPHOS display very similar geometries, while the electronic availability of the former is higher than that exhibited by the latter. The Rh and Ru complexes of UIluPHOS produced excellent enantiomeric excesses (98.9-99.5%) in the hydrogenation of N-acetyl-alpha-enamino acids and reaction rates higher than those found when employing the analogous complexes of Me-DuPHOS.

  DOI：

  10.1021/jo050390d

文献信息

• US7307037B2
  申请人：——

  公开号：US7307037B2

  公开（公告）日：2007-12-11
• 2,5-Dimethyl-3,4-bis[(2<i>R</i>,5<i>R</i>)-2,5-dimethylphospholano]thiophene:  First Member of the Hetero-DuPHOS Family
  作者：Tiziana Benincori、Tullio Pilati、Simona Rizzo、Franco Sannicolò、Mark J. Burk、Lorenzo de Ferra、Elio Ullucci、Oreste Piccolo

  DOI：10.1021/jo050390d

  日期：2005.7.1

  The 2,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholanolthiophene (UluPHOS), a new thiophene-based analogue of (RR)-1,2-bis(phospholano)benzene (Me-DuPHOS), was synthesized, geometrically and electronically characterized, and employed as ligand of Rh and Ru in some standard hydrogenation reactions of prostereogenic functionalized carbon-carbon and carbon-oxygen double bonds. The synthesis of UlluPHOS is much easier than that provided for Me-DuPHOS. UlluPHOS and Me-DuPHOS display very similar geometries, while the electronic availability of the former is higher than that exhibited by the latter. The Rh and Ru complexes of UIluPHOS produced excellent enantiomeric excesses (98.9-99.5%) in the hydrogenation of N-acetyl-alpha-enamino acids and reaction rates higher than those found when employing the analogous complexes of Me-DuPHOS.
• Process-Scale Total Synthesis of Nature-Identical (−)-(S,S)-7-Hydroxycalamenal in High Enantiomeric Purity through Catalytic Enantioselective Hydrogenation
  作者：Tiziana Benincori、Silvana Bruno、Giuseppe Celentano、Tullio Pilati、Alessandro Ponti、Simona Rizzo、Mara Sada、Francesco Sannicolò

  DOI：10.1002/hlca.200590139

  日期：2005.7

  A process-scale stereoselective synthesis of nature-identical (−)-(S,S)-7-hydroxycalamenal (=(−)-(5S,8S)-5,6,7,8-tetrahydro-3-hydroxy-5-methyl-8-(1-methylethyl)naphthalene-2-carbaldehyde; (−)-1a) in 96% enantiomeric excess (ee) with the aid of chiral Ru complexes has been developed. The key step was the enantioselective hydrogenation of easily accessible 2-(4-methoxyphenyl)-3-methylbut-2-enoic acid

  与自然界相同的（-）-（S，S）-7-羟基cal胺（=（-）-（5 S，8 S）-5,6,7,8-四氢-3-羟基借助手性Ru配合物，开发了96％对映异构体过量（ee）的-5-甲基-8-（1-甲基乙基）萘-2-甲醛；（-）- 1a）。关键步骤是将易于获得的2-（4-甲氧基苯基）-3-甲基丁-2-烯酸（10）在86％ee中对映体选择性氢化为（+）- 11（方案5和表1）。通过诱导中间体（+）-3,4-二氢-4-（1-甲基乙基）-7-甲氧基-2的结晶，光学纯度（96％ee）大大提高。H-萘-1-酮（（+）- 3）。对类似物（-）- 9进行的计算构象分析合理化了CC键催化加氢中获得的高非对映选择性。