(2S,5S)-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2S,5S)-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidine
• 英文别名: tert-butyl-[[(2S,5S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]pyrrolidin-2-yl]methoxy]-dimethylsilane
• 化学式: C₁₈H₄₁NO₂Si₂
• 分子量: 359.7
• InChiKey: PWORPPXSMZUJJJ-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.15
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,5S)-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidine 、 碘甲烷 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以88%的产率得到(2S,5S)-N,N'-dimethyl-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidinium iodide
  参考文献：
  名称：

  C2-Symmetric Pyrrolidine-Based Chiral Ammonium Salts as a Phase-Transfer Catalyst

  摘要：

  Chiral pyrrolidinium salts having substituents at the alpha, alpha' positions were synthesized to develop a chiral phase-transfer catalyst which have more simplified structure. The catalytic function of these synthesized catalysts was evaluated using asymmetric benzylation of N-(diphenylmethylene)glycine tert-butyl ester, and alpha,alpha'-disubstituded pyrrolidinium salts having an alkyl chain with a hydroxyl group at a chiral center were found to afford moderate enantioselectivity.

  DOI：

  10.3987/com-11-12254
• 作为产物：
  描述：

  1,2,5,6-四羟基己烷 在 咪唑 、 4-二甲氨基吡啶 、 palladium dihydroxide 、 氢气 、 三乙胺 作用下， 生成 (2S,5S)-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidine
  参考文献：
  名称：

  Symmetry-Assisted Synthesis of C₂-Symmetric trans-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes

  摘要：

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.

  DOI：

  10.1021/jo971995f
• 作为试剂：
  描述：

  2-((7-bromohept-2-yn-1-yl)oxy)tetrahydro-2H-pyran 在 Lindlar's catalyst 盐酸 、 manganese(IV) oxide 、 sodium azide 、 氢气 、 sodium sulfate 、 (2S,5S)-2,5-bis[tert-butyl(dimethyl)silyloxymethyl]pyrrolidine 作用下， 以 甲醇 、 乙醇 、 二甲基亚砜 、 乙酸乙酯 、 丙酮 、 甲苯 为溶剂， 20.0~100.0 ℃ 、101.33 kPa 条件下， 反应 55.0h， 生成 1,2,3,4,4a,8,9,10-octahydro-pyrido[1,2-a]quinolin-7-one
  参考文献：
  名称：

  A Formal [3 + 3] Cycloaddition Reaction. 5. An Enantioselective Intramolecular Formal Aza-[3 + 3] Cycloaddition Reaction Promoted by Chiral Amine Salts

  摘要：

  A detailed account on chiral secondary amine salt promoted enantioselective intramolecular formal aza-[3 + 3] cycloadditions is described here for the first time. The dependence of enantioselectivity on the structural feature of these chiral amines is thoroughly investigated. This study also reveals a very interesting reversal of the stereochemistry in the respective cycloadducts obtained using C-1- and C-2-symmetric amine salts. In addition, the influence of solvents, counteranions, and temperatures on the enantioselectivity is described, and a unified mechanistic model based on experimental results as well as semiempirical calculations is proposed.

  DOI：

  10.1021/jo050171s

文献信息

• Development of Guanidine-Bisurea Bifunctional Organocatalysts with a Chiral Pyrrolidine Moiety and Application to α-Hydroxylation of Tetralone-Derived β-Keto Esters
  作者：Minami Odagi、Kan Takayama、Makoto Sato、Masahiro Yamanaka、Kazuo Nagasawa

  DOI：10.3390/molecules200712590

  日期：——

  guanidine-bisurea bifunctional organocatalysts 5 bearing a chiral pyrrolidine moiety on guanidine were designed with the guidance of DFT calculations. The resulting organocatalysts 5 were examined for α-hydroxylation of tetralone-derived β-keto esters, and good selectivity was obtained with 5j bearing a methoxymethyl ether-containing chiral pyrrolidine moiety.

  在DFT计算的指导下，设计了在胍上带有手性吡咯烷部分的新型胍-双脲双功能有机催化剂5。检查得到的有机催化剂5的四氢萘酮衍生的β-酮酯的α-羟基化，并且用带有含甲氧基甲基醚的手性吡咯烷部分的5j获得了良好的选择性。
• An Unexpected Carbon Dioxide Insertion in the Reaction of Trans-2,4-Disubstituted Azetidine, Trans-2,5-Disubstituted Pyrrolidine, or Trans-2,6-Disubstituted Piperidine with Diphenylthiophosphinic Chloride and Diphenylselenophosphinic Chloride
  作者：Min Shi、Jian-Kang Jiang、Yu-Mei Shen、Yan-Shu Feng、Gui-Xin Lei

  DOI：10.1021/jo991985+

  日期：2000.6.1

  In the reaction of trans-2,4-disubstituted azetidine, trans-2, 5-disubstituted pyrrolidine, or trans-2,6-disubstituted piperidine with diphenylthiophosphinic chloride or diphenylselenophosphinic chloride in acetonitrile in the presence of potassium carbonate at room temperature, an unexpected carbon dioxide insertion produced carbamic diphenylthiophosphinic or diphenylselenophosphinic anhydride in

  在室温下，在碳酸钾存在下，反式2,4-二取代的氮杂环丁烷，反式-2、5-二取代的吡咯烷或反式的2,6-二取代的哌啶与二苯硫代次膦酰氯或二苯基硒代次膦酰氯在乙腈中反应，意外的二氧化碳插入会以良好的收率产生氨基甲酸二苯硫代次膦酸酯或二苯基硒代次膦酸酐。当反应在二氧化碳气氛下使用氢氧化钾或三乙胺作为碱进行反应时，也可以获得相同的产物。这是一个非常简单的反应过程，与没有金属催化剂的情况下固定二氧化碳有关。
• Symmetry-Assisted Synthesis of <i>C</i>₂-Symmetric <i>trans</i>-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes
  作者：Hiroki Takahata、Seiki Takahashi、Shin-ichi Kouno、Takefumi Momose

  DOI：10.1021/jo971995f

  日期：1998.4.1

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.
• C2-Symmetric Pyrrolidine-Based Chiral Ammonium Salts as a Phase-Transfer Catalyst
  作者：Takashi Itoh、Tatsuya Ishikawa、Kazuhiro Nagata、Sachiko Kani、Mamoru Matsuo、Daisuke Sano、Takuya Kanemitsu、Michiko Miyazaki

  DOI：10.3987/com-11-12254

  日期：——

  Chiral pyrrolidinium salts having substituents at the alpha, alpha' positions were synthesized to develop a chiral phase-transfer catalyst which have more simplified structure. The catalytic function of these synthesized catalysts was evaluated using asymmetric benzylation of N-(diphenylmethylene)glycine tert-butyl ester, and alpha,alpha'-disubstituded pyrrolidinium salts having an alkyl chain with a hydroxyl group at a chiral center were found to afford moderate enantioselectivity.