(cyclohexyloxy)dimethylallylsilane | 81194-47-0

• 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
• 英文名称: (cyclohexyloxy)dimethylallylsilane
• 英文别名: Allyl(cyclohexyloxy)dimethylsilane；cyclohexyloxy-dimethyl-prop-2-enylsilane
• CAS: 81194-47-0
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: JFHPCGANYAOIDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  Propionic acid (S)-6-oxo-1-phenyl-hexyl ester 、 (cyclohexyloxy)dimethylallylsilane 在 三氟化硼乙醚 正丁基锂 、 (+)-β-chlorodiisopinocampheylborane 、 sodium t-butanolate 、 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 20.0h， 生成 [(1S,6S,7R)-6,7-dihydroxy-1-phenylnon-8-enyl] propanoate
  参考文献：
  名称：

  Studies toward Soraphen A:  An Aldol−Metathesis Avenue to the Macrocyclic Framework

  摘要：

  We describe a convergent approach to soraphen A, 1, that involves coupling of two fragments by an aldol condensation - olefin metathesis sequence. This route permits rapid access to congeners of 1.

  DOI：

  10.1021/ol060882s
• 作为产物：
  描述：

  烯丙基二甲基氯硅烷 在 正丁基锂 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 生成 (cyclohexyloxy)dimethylallylsilane
  参考文献：
  名称：

  4,5-Diisopropyl-B-[(E)-[(3‘-menthofuryl)dimethylsilyl]allyl]-1,3,2- dioxaborolane, an Improved Chiral Reagent for the Anti α-Hydroxyallylation of Aldehydes:  Application to the Enantioselective Synthesis of (−)-Swainsonine

  摘要：

  Diisopropyl tartrate-modified (E)-[gamma-(furyldimethylsilyl)allyl]boronates 10 and 11 were designed for the enantioselective synthesis of substituted anti-3,4-dihydroxy-1-butenes 9 via the anti-alpha-hydroxyallylation of aldehydes. The reactions of aldehydes with 10 and 11 provided furyldimethylsilyl-substituted anti-1,2-silanols 12 and 13 with good enantioselectivity (74-82% ee), and the silanols were oxidized to the corresponding anti-1,2-diols 9 by a modified Fleming-Tamao oxidation protocol. The high reactivity of the (menthofuryl)silane unit toward electrophilic substitution allowed complete protodesilylation of menthofuryl-substituted silanols 13 and subsequent oxidation to diols 9 in a one-pot operation without competing protodesilylation of the allylsilane unit. However, a two-step protocol was required for the protodesilylation-oxidation of the less reactive 2-(5-methyl)-asymmetric reactions with three chiral aldehydes 23-35 (80 to >92% de, with the exception of the mismatched reactions with aldehyde 25, which were essentially unselective). However, [[[2-(5-methylfuryl)]dimethylsilyl]ally]boronate 10 could only be synthesized in less than or equal to 15% yield, and oxidations of the 2-(5-methylfuryl)-substituted silanols 12 were lower-yielding than oxidations of the corresponding menthofuryl-substituted silanols 13. Thus diisopropyl tartrate-modified (E)-[gamma-[(menthofuryl)dimethylsilyl]ally]boronate 11 proved to be the more useful of the two reagents. As a demonstration of the utility of 11 in the synthesis of polyhydroxylated natural products, this new reagent was used in a brief and highly stereoselective synthesis of the naturally occurring alkaloid (-)-swainsonine (42).

  DOI：

  10.1021/jo961840s

文献信息

• Diisopropyl tartrate modified (E)-γ-[(cyclohexyloxy)dimethylsilyl-allylboronate, a chiral reagent for the stereoselective synthesis of anti 1,2-diols via the formal α-hydroxyallylation of aldehydes
  作者：William R. Roush、Paul T. Gover、Xiaofa Lin

  DOI：10.1016/s0040-4039(00)97299-x

  日期：1990.1

  An enantioselective synthesis of anti 1,2-diols via the reactions of aldehydes and the tartrate ester modified γ(alkoxysilyl)allylboronate2 has been developed. This method is most effective in double asymmetric reactions with chiral aldehydes.

  已经开发了通过醛与酒石酸酯改性的γ（烷氧基甲硅烷基）烯丙基硼酸酯2的反应，对映选择性合成抗1，2-二醇的方法。该方法在与手性醛的双重不对称反应中最有效。
• The study of intramolecular tandem radical cyclizations of acylsilanes with radicalphiles attached on silicon
  作者：Kuo-Hsiang Tang、Fang-Yu Liao、Yeun-Min Tsai

  DOI：10.1016/j.tet.2004.12.053

  日期：2005.2

  Radical cyclizations of acylsilanes with radicalphilic pendant introduced on silicon proceeded in a tandem fashion to give spiro products containing a cyclic silyl ether skeleton. Because the alkoxysilyl group can be replaced with a hydroxy group through oxidation, the spiro silyl ethers can be converted into diols. In the case with a radical intermediate carrying 2-oxa-3-sila-6-heptenyl skeleton,

  带有在硅上引入的具有自由基的侧基的酰基硅烷的自由基环化以串联方式进行，以得到含有环状甲硅烷基醚骨架的螺环产物。因为烷氧基甲硅烷基可以通过氧化被羟基取代，所以螺硅烷基醚可以转化为二醇。在与自由基中间输送2-氧杂-3-硅杂-6-庚烯基骨架的情况下，产品从1,7-衍生内环化反应以良好产率获得。
• Group transfer from silicon to carbon via tandem radical cyclizations of acylsilanes
  作者：Yeun-Min Tsai、Kuo-Hsiang Tang、Weir-Torn Jiaang

  DOI：10.1016/0040-4039(96)01773-x

  日期：1996.10

  Tandem radical cyclizations of acylsilanes with alkene or alkyne functionalities attached to silicon afforded cyclic silyl ethers which were oxidatively hydrolyzed to give diols or ketone alcohols.

  具有连接到硅上的烯烃或炔烃官能团的酰基硅烷的串联自由基环化提供了环状甲硅烷基醚，其被氧化水解以得到二醇或酮醇。
• Reductive alkylation/arylation of arylcarbinols and ketones with organosilicon compounds
  作者：J. A. Cella

  DOI：10.1021/jo00132a027

  日期：1982.5
• 4,5-Diisopropyl-<i>B</i>-[(<i>E</i>)-[(3‘-menthofuryl)dimethylsilyl]allyl]-1,3,2- dioxaborolane, an Improved Chiral Reagent for the Anti α-Hydroxyallylation of Aldehydes:  Application to the Enantioselective Synthesis of (−)-Swainsonine
  作者：J. A. Hunt、William R. Roush

  DOI：10.1021/jo961840s

  日期：1997.2.1

  Diisopropyl tartrate-modified (E)-[gamma-(furyldimethylsilyl)allyl]boronates 10 and 11 were designed for the enantioselective synthesis of substituted anti-3,4-dihydroxy-1-butenes 9 via the anti-alpha-hydroxyallylation of aldehydes. The reactions of aldehydes with 10 and 11 provided furyldimethylsilyl-substituted anti-1,2-silanols 12 and 13 with good enantioselectivity (74-82% ee), and the silanols were oxidized to the corresponding anti-1,2-diols 9 by a modified Fleming-Tamao oxidation protocol. The high reactivity of the (menthofuryl)silane unit toward electrophilic substitution allowed complete protodesilylation of menthofuryl-substituted silanols 13 and subsequent oxidation to diols 9 in a one-pot operation without competing protodesilylation of the allylsilane unit. However, a two-step protocol was required for the protodesilylation-oxidation of the less reactive 2-(5-methyl)-asymmetric reactions with three chiral aldehydes 23-35 (80 to >92% de, with the exception of the mismatched reactions with aldehyde 25, which were essentially unselective). However, [[[2-(5-methylfuryl)]dimethylsilyl]ally]boronate 10 could only be synthesized in less than or equal to 15% yield, and oxidations of the 2-(5-methylfuryl)-substituted silanols 12 were lower-yielding than oxidations of the corresponding menthofuryl-substituted silanols 13. Thus diisopropyl tartrate-modified (E)-[gamma-[(menthofuryl)dimethylsilyl]ally]boronate 11 proved to be the more useful of the two reagents. As a demonstration of the utility of 11 in the synthesis of polyhydroxylated natural products, this new reagent was used in a brief and highly stereoselective synthesis of the naturally occurring alkaloid (-)-swainsonine (42).