(R,R)-bis[o-[1-(dimethylamino)ethyl]phenyl] diselenide | 172842-09-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (R,R)-bis[o-[1-(dimethylamino)ethyl]phenyl] diselenide
• 英文别名: (1R)-1-[2-[[2-[(1R)-1-(dimethylamino)ethyl]phenyl]diselanyl]phenyl]-N,N-dimethylethanamine
• CAS: 172842-09-0
• 化学式: C₂₀H₂₈N₂Se₂
• 分子量: 454.376
• InChiKey: YVRKOVPFNYBODE-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.21
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R,R)-bis[o-[1-(dimethylamino)ethyl]phenyl] diselenide 在 溴 作用下， 以 四氯化碳 、 乙醚 为溶剂， 反应 4.33h， 生成
  参考文献：
  名称：

  Asymmetric Addition Reactions with Optimized Selenium Electrophiles

  摘要：

  AbstractThe synthesis of various nonracemic diselenides by different methods is described. These diselenides are precursors for optically active selenium electrophiles. Their facial selectivity upon addition to styrene was investigated with respect to the chiral moiety neighboring the selenium. Diselenides 1 i, 1 n, and 1 v yielded addition products 7 with diastereomeric excesses up to 95%. Some diselenides, intermediates, and products of the addition reaction were investigated by 77Se NMR spectroscopy.

  DOI：

  10.1002/chem.19970031123
• 作为产物：
  描述：

  (R)-(+)-N,N-二甲基-1-苯乙胺 在 selenium 、 叔丁基锂 作用下， 生成 (R,R)-bis[o-[1-(dimethylamino)ethyl]phenyl] diselenide
  参考文献：
  名称：

  苄胺的手性二硒化物：乙醛中二乙基锌的催化剂

  摘要：

  通过短的合成序列（方案1）制备了一系列在侧链中具有N原子的新的手性二硒化物。这些二硒化物中只有1 mol％非常有效地催化了二乙基锌与各种芳香族和α，β-不饱和醛的加成反应，从而产生了高达98％ee的仲醇（流程2和表1和表2）。用这些催化剂观察到不对称扩增。进行了详细的NMR研究以表征催化活性物质。

  DOI：

  10.1002/hlca.19960790718

文献信息

• Asymmetric methoxyselenenylation of alkyl vinyl ethers: a new route to chiral acetals
  作者：Masahiko Uchiyama、Shinya Satoh、Akihiro Ohta

  DOI：10.1016/s0040-4039(00)02285-1

  日期：2001.2

  The asymmetric methoxyselenenylation of alkyl vinyl ethers afforded the corresponding chiral acetals with moderate to good diastereoselectivity. This reaction and subsequent deselenenylation provided a new method of preparing enantiomerically enriched acetals in which the acetal carbon was the only stereogenic center.

  烷基乙烯基醚的不对称甲氧基硒烯基化得到相应的手性缩醛，具有中等至良好的非对映选择性。该反应和随后的去硒烯基化提供了一种制备对映体富集的缩醛的新方法，其中缩醛碳是唯一的立体异构中心。
• Chiral Diselenides from Benzylamines: Catalysts in the Diethylzinc Addition to Aldehydes
  作者：Thomas Wirth、Klaus J. Kulicke、Gianfranco Fragale

  DOI：10.1002/hlca.19960790718

  日期：1996.10.30

  synthetic sequence (Scheme 1). Only 1 mol-% of these diselenides catalyzed very effectively the diethylzinc addition to various aromatic and α,β-unsaturated aldehydes yielding the secondary alcohols in up to 98% ee (Scheme 2 and Tables 1 and 2). An asymmetric amplification was observed with these catalysts. Detailed NMR studies were performed to characterize the catalytically active species.

  通过短的合成序列（方案1）制备了一系列在侧链中具有N原子的新的手性二硒化物。这些二硒化物中只有1 mol％非常有效地催化了二乙基锌与各种芳香族和α，β-不饱和醛的加成反应，从而产生了高达98％ee的仲醇（流程2和表1和表2）。用这些催化剂观察到不对称扩增。进行了详细的NMR研究以表征催化活性物质。
• A New Entry to Enantioselective Synthesis of .ALPHA.-Methylene-.BETA.-hydroxy Ketones by the Chalcogeno-Baylis-Hillman Reaction.
  作者：Tetsuo IWAMA、Shin-ichiro TSUJIYAMA、Hironori KINOSHITA、Kiyoko KANEMATSU、Yasuo TSURUKAMI、Tatsunori IWAMURA、Shin-ichi WATANABE、Tadashi KATAOKA

  DOI：10.1248/cpb.47.956

  日期：——

  Chiral hydroxy chalcogenides in the presence of TiCl4 achieved the asymmetric version of the chalcogeno-Baylis-Hillman reaction. The reaction proceeded under atmospheric pressure for 1h. 10-Methylthioisoborneol (9) achieved the best enantioselectivity. A methoxy derivative 10 of 10-methylthioisoborneol resulted in lower-selectivity than that obtained by 10-methylthioisoborneol (9). A hydroxyl group is required to perform good asymmetric induction. The asymmetric chalcogeno-Baylis-Hillman reaction with a C2 symmetric bidentate ligand-TiCl4 complex was also examined. Diol ligands gave the adduct in low to good yields with low or no enantiomeric excess. The adduct was also obtained in low to high yields with low or no enantiomeric excess using bisoxazoline ligands.

  在 TiCl4 的存在下，手性羟基卤代烃实现了不对称版的卤代烃-Baylis-Hillman 反应。反应在常压下进行了 1 小时。10-Methylthioisoborneol (9) 的对映选择性最好。10-Methylthioisoborneol 的甲氧基衍生物 10 的选择性低于 10-Methylthioisoborneol (9)。羟基是进行良好不对称诱导的必要条件。此外，还研究了与 C2 对称双齿配体-TiCl4 复合物的不对称缩醛-Baylis-Hillman 反应。二元醇配体的加合物产率从低到高不等，对映体过量率较低或没有对映体过量。使用双噁唑啉配体也能以低产率到高产率获得加合物，对映体过量率较低或没有对映体过量。
• A simple enantioselective synthesis of (R)- and (S)-1,7-dioxaspiro[5.5]undecane via intramolecular asymmetric oxyselenenylation: a new route to optically active spiroketals
  作者：Masahiko Uchiyama、Masako Oka、Satohide Harai、Akihiro Ohta

  DOI：10.1016/s0040-4039(01)00024-7

  日期：2001.3

  Both enantiomers of 1,7-dioxaspiro[5.5]undecane, the major pheromone components of the olive fruit fly (Bactrocea oleae), have been synthesized by using a new method based on the intramolecular asymmetric oxyselenenylation of 4-(3,4-dihydro-2H-pyran-6-yl)butan-1-ol.

  橄榄果蝇（Bactrocea oleae）的主要信息素成分1,7-二氧杂螺[5.5]十一烷的两种对映异构体均采用基于4-（3,4-二氢分子内不对称氧硒烯化的新方法）合成-2 H -pyran-6-yl）butan-1-ol。
• Asymmetric Addition Reactions with Optimized Selenium Electrophiles
  作者：Thomas Wirth、Gianfranco Fragale

  DOI：10.1002/chem.19970031123

  日期：1997.11

  AbstractThe synthesis of various nonracemic diselenides by different methods is described. These diselenides are precursors for optically active selenium electrophiles. Their facial selectivity upon addition to styrene was investigated with respect to the chiral moiety neighboring the selenium. Diselenides 1 i, 1 n, and 1 v yielded addition products 7 with diastereomeric excesses up to 95%. Some diselenides, intermediates, and products of the addition reaction were investigated by 77Se NMR spectroscopy.