(9CI)-(环戊基氧基)(1,1-二甲基乙基)二甲基-硅烷 | 135746-46-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: (9CI)-(环戊基氧基)(1,1-二甲基乙基)二甲基-硅烷
• 英文名称: 1-(t-butyldimethylsilyl)cyclopentanol
• 英文别名: tert-butyl(cyclopentyloxy)dimethylsilane；Cyclopentanol, DMTBS；tert-butyl-cyclopentyloxy-dimethylsilane
• CAS: 135746-46-2
• 化学式: C₁₁H₂₄OSi
• 分子量: 200.396
• InChiKey: BDJHAGOROXVJFV-UHFFFAOYSA-N

物化性质

• 保留指数：
  1119

计算性质

• 辛醇/水分配系数(LogP)：
  3.95
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (9CI)-(环戊基氧基)(1,1-二甲基乙基)二甲基-硅烷 在 sulfonic acid functionalized nanoporous silica 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以90%的产率得到环戊醇
  参考文献：
  名称：

  A high loading sulfonic acid-functionalized ordered nanoporous silica as an efficient and recyclable catalyst for chemoselective deprotection of tert-butyldimethylsilyl ethers

  摘要：

  A high loading sulfonic acid-functionalized ordered nanoporous silica efficiently catalyzes the deprotection of a variety of alcoholic TBDMS (tert-butyldimethylsilyl)ethers in methanol. The catalyst shows high thermal stability (up to 240 degrees C) and can be recovered and reused for at least seven reaction cycles without loss of reactivity. This method can be used to deprotect TBDMS ethers of alcohols in the presence of TBDMS ethers of phenols. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.04.100
• 作为产物：
  描述：

  2-(叔丁基二甲基甲硅烷基)-1,3-二噻烷 在 正丁基锂 、 偶氮二异丁腈 、 Celite 、 三氟化硼乙醚 、 三正丁基氢锡 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 生成 (9CI)-(环戊基氧基)(1,1-二甲基乙基)二甲基-硅烷
  参考文献：
  名称：

  Intramolecular free radical cyclizations using acylsilanes as radicalphiles

  摘要：

  Carbon radicals add intramolecularly to acylsilanes at the carbonyl carbon followed by radical Brook rearrangement to give silylated cyclopentanols or cyclohexanols in good yields.

  DOI：

  10.1016/0040-4039(91)80820-v

文献信息

• The photolytic and hydrolytic lability of sisyl (Si(SiMe3)3) ethers, an alcohol protecting group
  作者：Michael A. Brook、Sonya Balduzzi、Mustafa Mohamed、Christine Gottardo

  DOI：10.1016/s0040-4020(99)00562-1

  日期：1999.8

  The tris(trimethylsilyl)silyl (sisyl) group is a photolabile protecting group for primary and secondary alcohols. Sisyl (tris(trimethylsilyl)silyl) ethers 2b–11b of a number of primary and secondary alcohols 2a–11a were prepared in yields ranging from 70–97%. The resulting silyl ethers were stable to aqueous bases, Grignard reagents and Wittig reagents as would be expected for bulky alkoxysilanes.

  三（三甲基甲硅烷基）甲硅烷基（甲硅烷基）是伯醇和仲醇的光不稳定保护基。多种伯醇和仲醇2a-11a中的甲硅烷基（三（三甲基甲硅烷基）甲硅烷基）醚2b-11b制备的产率在70-97％之间。生成的甲硅烷基醚对水性碱，格利雅试剂和维蒂希试剂稳定，这是对大体积烷氧基硅烷所期望的。它们对包括CsF在内的选定氟化物盐也稳定。可以在30分钟内使用254 nm的光解裂解甲硅烷基醚，得到起始醇的产率为62-95％。使用2,3-二甲基-1,3-丁二烯作为甲硅烷基阱，对甲硅烷基醚的光解行为进行了更详细的研究。寡硅烷片段化为亚甲硅的区域化学性质显示取决于烷氧基。三个sisyl醚的水解稳定性与类似比较吨-丁基二甲基甲硅烷基醚。可以通过选择溶剂来改变两个甲硅烷基的相对稳定性：在乙酸/水中，易于水解的顺序为：ROSi（SiMe 3）3 > ROSiMe 2 t -Bu ；使用p -TsOH·H 2 O在CDCl 3中观察到相反的顺序。在AcOH
• Alkoxyallylsilanes: Functional Protecting Groups
  作者：Sonya Balduzzi、Michael A. Brook

  DOI：10.1016/s0040-4020(99)01062-5

  日期：2000.3

  Allyl-t-butylmethylsilyl groups were shown to function as alcohol protecting groups whose hydrolytic stability was greater than t-butyldimethylsilyl (TBS) and Si(SiMe3)(3) (sisyl) groups. Pseudo-first-order rate constants for the acidic hydrolysis of primary, benzylic, and secondary allyl-t-butylmethylsilyl ethers in AcOD/THF-d(8)/D2O were determined to be 2.94x10(-3), 8.26x10(-4), and 8.26x10(-4)s(-1) respectively. The regioselectivity of acidic hydrolysis of allylbenzyloxy-t-butylmethylsilane 1 was examined under strong acid (p-TsOH/ CD2Cl2) and weak acid (AcOD/HF-d(8)/D2O) conditions. In both cases, benzyl alcohol was initially produced exclusively from silicon-oxygen bond cleavage: allylic cleavage was only subsequently observed over time. However, the allyl group of the silyl ether could be hydrosilylated. The resulting alkoxy-functionalized disiloxane had greater hydrolytic stability under acidic conditions than the starting alkoxyallyl-t-butylmethylsilane. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Cobalt-Mediated Diastereoselective Cross-Coupling Reactions between Cyclic Halohydrins and Arylmagnesium Reagents
  作者：Jeffrey M. Hammann、Andreas K. Steib、Paul Knochel

  DOI：10.1021/ol503361m

  日期：2014.12.19

  Cyclic TBS-protected iodohydrins (and bromohydrins) undergo a highly diastereoselective cross-coupling with various aryl- and heteroarylmagnesium reagents in the presence of THF-soluble CoCl2.2LiCl and TMEDA as a ligand leading to trans-2-arylcyclohexanol derivatives in good yields and dr up to >99:1. A range of functional groups are tolerated in the Grignard reagent (e.g., COOR, CN, CF3, SF5). The use of heterocyclic iodohydrins leads to trans-3,4-disubstituted pyrrolidines and tetrahydrofurans.
• The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals
  作者：Sheng-Yueh Chang、Weir-Torn Jiaang、Chaur-Donp Cherng、Kuo-Hsiang Tang、Chih-Hao Huang、Yeun-Min Tsai

  DOI：10.1021/jo9711302

  日期：1997.12.1

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.