(S)-3-<(tert-butyldimethylsiloxy)methyl>-3,4-dihydroisoquinoline | 123475-83-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢异喹啉
• 英文名称: (S)-3-<(tert-butyldimethylsiloxy)methyl>-3,4-dihydroisoquinoline
• 英文别名: (S)-3-(((tert-butyldimethylsilyl)oxy)methyl)-3,4-dihydroisoquinoline；(S)-3-tert-butyldimethylsiloxymethyl-3,4-dihydroisoquinoline；(S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline；tert-butyl-[[(3S)-3,4-dihydroisoquinolin-3-yl]methoxy]-dimethylsilane
• CAS: 123475-83-2
• 化学式: C₁₆H₂₅NOSi
• 分子量: 275.466
• InChiKey: PXAWYDLLNVNAPZ-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-3-<(tert-butyldimethylsiloxy)methyl>-3,4-dihydroisoquinoline 在 sodium tungstate 、 双氧水 作用下， 以 甲醇 、 水 为溶剂， 以57%的产率得到(S)-3-(((tert-butyldimethylsilyl)oxy)methyl)-3,4-dihydroisoquinoline 2-oxide
  参考文献：
  名称：

  通过L-苯丙氨酸衍生的二氢异喹啉N-氧化物立体选择性合成1,3-二取代的二氢异喹啉

  摘要：

  描述了手性池衍生的硝酮3的制备及其在无保护基的立体选择性合成一系列1,3-二取代的四氢异喹啉中的用途。将格氏试剂添加到硝酮3中产生具有良好选择性的反式-1，3-二取代的N-羟基四氢异喹啉6，而向该硝酮的1，3-偶极环加成提供了作为单一非对映异构体的3-（2-羟基烷基）异喹啉12。

  DOI：

  10.1039/c8ob02007h
• 作为产物：
  描述：

  (3S)-3-(tert-butyldimethylsilyloxymethyl)-1,2,3,4-tetrahydroisoquinoline 在 氢氧化钾 、 N-氯代丁二酰亚胺 、 四丁基碘化铵 作用下， 生成 (S)-3-<(tert-butyldimethylsiloxy)methyl>-3,4-dihydroisoquinoline
  参考文献：
  名称：

  A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)

  摘要：

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.

  DOI：

  10.1021/jo00057a028

文献信息

• Enantioselective deprotonation of 4-tert-butylcyclohexanone by conformationally constrained chiral lithium amide bases
  作者：Varinder K. Aggarwal、Paul S. Humphries、Ashley Fenwick

  DOI：10.1039/a905947d

  日期：——

  Conformationally rigid chiral lithium amides based on a tetrahydroisoquinoline motif have been prepared bearing a range of substituents at C1 and C3. These bases were tested in the asymmetric deprotonation reaction of 4-tert-butylcyclohexanone. Although the 1-substituted tetrahydroisoquinolines gave low enantioselectivity, the chiral bases containing a nitrogen heterocycle at C3 were found to induce

  已经制备了基于四氢异喹啉基序的构象刚性的手性锂酰胺，其在C1和C3处带有一系列取代基。在4-叔丁基环己酮的不对称去质子反应中测试了这些碱。尽管1-取代的四氢异喹啉具有较低的对映选择性，但发现在HMPA存在下，在C3处含有氮杂环的手性碱可诱导较高的对映选择性（81％ee）。
• Intermolecular Regio‐ and Stereoselective Hetero‐[5+2] Cycloaddition of Oxidopyrylium Ylides and Cyclic Imines
  作者：Changgui Zhao、Daniel A. Glazier、Daoshan Yang、Dan Yin、IIia A. Guzei、Michael M. Aristov、Peng Liu、Weiping Tang

  DOI：10.1002/anie.201811896

  日期：2019.1.14

  We have developed the first intermolecular hetero‐[5+2] cycloaddition reaction between oxidopyrylium ylides and cyclic imines with excellent control of regio‐ and stereoselectivity. Surprisingly, divergent stereochemistry was observed depending on the substitution pattern of the oxidopyrylium ylide. This new reaction provides quick access to highly substituted nitrogen‐containing seven‐membered rings—azepanes

  我们开发了第一个分子间异[5 + 2]环氧化吡啶鎓和环状亚胺之间的杂分子间[5 + 2]环加成反应，可很好地控制区域选择性和立体选择性。出乎意料的是，根据氧化吡啶鎓叶立德的取代模式观察到不同的立体化学。这种新的反应使人们可以快速进入高度取代的含氮七元环-氮杂环丁烷。值得注意的是，广泛的氧化吡啶鎓基团和环状亚胺参与了这种新型的异[5 + 2]环加成反应，并且环加合物可以轻松转化为生物活性天然产物的核心骨架。DFT计算表明，环加成反应通过逐步途径进行，亚胺氮原子充当亲核试剂以引发环加成反应。
• High 1,3-Asymmetric Induction in Addition of Allylic Tin Reagents to Chiral 3-Substituted 3,4-Dihydroisoquinolines Activated by Acyl Chlorides
  作者：Bunpei Hatano、Yoshikazu Haraguchi、Sinpei Kozima、Ryohei Yamaguchi

  DOI：10.1246/cl.1995.1003

  日期：1995.11

  Nucleophilic addition reactions of allylic tin reagents to chiral 3-substituted 3,4-dihydroisoquinolines activated by acyl chlorides afford anti 1,3-disubstituted 1,2,3,4-tetrahydroisoquinolines stereoselectively through high 1,3-asymmetric induction.

  烯丙基锡试剂与酰氯活化的手性 3-取代 3,4-二氢异喹啉的亲核加成反应通过高 1,3-不对称诱导立体选择性地提供抗 1,3-二取代 1,2,3,4-四氢异喹啉。
• A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)
  作者：Ryohei Yamaguchi、Takashi Hamasaki、Tohru Sasaki、Tetsuo Ohta、Kiitiro Utimoto、Sinpei Kozima、Hidemasa Takaya

  DOI：10.1021/jo00057a028

  日期：1993.2

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.
• Stereoselective synthesis of 1,3-disubstituted dihydroisoquinolines <i>via</i><scp>l</scp>-phenylalanine-derived dihydroisoquinoline <i>N</i>-oxides
  作者：Jesús Flores-Ferrándiz、Nicholas Carter、Maria José González-Soria、Malgorzata Wasinska、Daniel Gill、Beatriz Maciá、Vittorio Caprio

  DOI：10.1039/c8ob02007h

  日期：——

  The preparation of chiral pool-derived nitrone 3 and its use in the protecting-group free, stereoselective synthesis of a range of 1,3-disubstituted tetrahydroisoquinolines is described. Grignard reagent additions to nitrone 3 yielded trans-1,3-disubstituted N-hydroxytetrahydroisoquinolines 6 with good levels of selectivity, while 1,3-dipolar cycloadditions to this nitrone provided access to 3-(2-

  描述了手性池衍生的硝酮3的制备及其在无保护基的立体选择性合成一系列1,3-二取代的四氢异喹啉中的用途。将格氏试剂添加到硝酮3中产生具有良好选择性的反式-1，3-二取代的N-羟基四氢异喹啉6，而向该硝酮的1，3-偶极环加成提供了作为单一非对映异构体的3-（2-羟基烷基）异喹啉12。