Chlor-2-furanyl-dimethylsilan | 183118-43-6

• 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: Chlor-2-furanyl-dimethylsilan
• 英文别名: (2-furyl)dimethylchlorosilane；Chloro-(furan-2-yl)-dimethylsilane；chloro-(furan-2-yl)-dimethylsilane
• CAS: 183118-43-6
• 化学式: C₆H₉ClOSi
• 分子量: 160.675
• InChiKey: YBUXSTJMAHJBPG-UHFFFAOYSA-N

物化性质

• 沸点：
  163.1±13.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.93
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Chlor-2-furanyl-dimethylsilan 在 三乙胺 作用下， 以 乙醚 为溶剂， 125.0 ℃ 、1000.0 MPa 条件下， 反应 31.5h， 生成 endo-3,12-dioxa-2,2-dimethyl-2-silatetracyclo[7.2.1.0^1,70^5,7]dodec-10-ene
  参考文献：
  名称：

  Intramolecular Diels-Alder reactions of furans with a merely strain-activated tetrasubstituted alkene: Bicyclopropylidene

  摘要：

  Bicyclopropylidene derivatives 1, 6, 8 with furan moieties attached on tethers of various length and nature all undergo clean intramolecular Diels-Alder reactions with complete endo-diastereoselectivities when heated to 70 - 130 degrees C, under 10 kbar pressure. The reaction rates are at]east as high or higher than those of analogously tethered methylenecyclopropane-furan derivatives 15, 17, 20, in spite of the fact that the reactive double bond in bicyclopropylidene is tetrasubstituted and not activated by any electron withdrawing group. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0040-4020(96)00720-x
• 作为产物：
  描述：

  2-溴呋喃 、 二氯二甲基硅烷 在 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 20.0h， 生成 Chlor-2-furanyl-dimethylsilan
  参考文献：
  名称：

  通过硅酸双胍离子对对酰基硅烷进行对映选择性 1,2-阴离子重排

  摘要：

  报道了高度对映选择性双胍催化的酰基硅烷串联重排。通过在硅上添加氟化物来活化酰基硅烷以形成五配位阴离子硅酸盐中间体。然后硅酸盐经历烷基或芳基从硅原子迁移到相邻的羰基碳原子（1,2-阴离子重排），然后进行 [1,2]-布鲁克重排，以高产率提供具有优异对映选择性的仲醇（高达 95% ee）。α-甲硅烷基甲醇中间体的分离以及 DFT 计算表明，1,2-阴离子重排是通过双胍硅酸盐离子对发生的，这是立体确定步骤。然后通过随后的 [1,2]-布鲁克重排保留形成的手性中心而不发生反转。巴豆酰基硅烷顺利转化为高烯丙基线性巴豆醇，保留 E/Z 几何结构，未检测到支链醇。这清楚地表明 1,2-阴离子重排是通过三元而不是五元过渡态发生的。

  DOI：

  10.1021/jacs.7b13056

文献信息

• Silylfurane und Bis(silyl)butadiine -Synthese, Lithiumderivate, Kristallstrukturen/ Silylfurans and Bis(silyl)butadiynes - Synthesis, Lithium Derivatives, Crystal Structures
  作者：Peter Neugebauer、Uwe Klingebiel、Mathias Noltemeyer

  DOI：10.1515/znb-2000-1005

  日期：2000.10.1

  Furan reacts with BuLi and halosilanes to give mono- (1, 5, 7), bis- (2, 6), tris- (3), and tetrakis(2-furanyl)silanes (4); (Fu-R; R = SiMe₂Cl (1), SiisoPr₂F (5), Si^tBu₂F (7); Fu-R-Fu; R = SiMe₂ (2), SiisoPr₂ (6); Fu₃Si^tBu (3), Fu₄Si (4)), 2,5-Bis(silyl)furans (8, 9) are obtained in the reaction of dilithiated furan and fluorosilanes in a molar ratio 1:2 (R-Fu-R; R = SiisoPr₂F (8), Si^tBu₂F (9), 1,4-Bis(di-tert-butylfluorosilyl)butadiyne (10) is formed from furan four equivalents of BuLi, and two equivalents of F₂Si^tBu₂. 10 reacts with KOH to give ^tBu₂(OH )Si-C =C -C =C-Si^tBu₂OH (11). Substitution of the fluorine atoms of 5 and 7 by a NH₂ group occurs with MNH₂ (M = Li, Na). 12 and 13 are obtained. The reaction of 13 with BuLi and ^tBu₂SiF₂ leads to the formation of FuSi^tBu₂NHSi^tBu₂F (14) and ^tBu₂Si(NH-Si^tBu₂Fu)₂ (15). The lithium derivative of 14 crystallizes as monomer from THF as FuSi^tBu₂N(LiTHF₂)Si^tBu₂F and as a dimer containing a four-membered ring (16) from n-hexane (FuSi^tBu₂NSi^tBu₂LiF)₂ (17). The crystal structures of 4, 10, 16,17 have been determined.

  摘要：Furan与BuLi和卤代硅烷反应，得到单-(1, 5, 7)、双-(2, 6)、三-(3)和四-(2-呋喃基)硅烷(4)；在二锂化呋喃和氟硅烷的反应中以1:2的摩尔比获得2,5-双(硅烷基)呋喃(8, 9)（R-Fu-R；R = SiisoPr2F(8)、Si t Bu2F(9)）；1,4-双(二叔丁基氟硅基)丁二炔(10)由呋喃四当量的BuLi和两当量的F2Si t Bu2形成。 10与KOH反应生成tBu2(OH)Si-C=C-C=C-SitBu2OH(11)。用MNH2(M = Li, Na)取代5和7的氟原子得到12和13。13与BuLi和tBu2SiF2反应形成FuSitBu2NHSitBu2F(14)和tBu2Si(NH-SitBu2Fu)2(15)。14的锂衍生物以FuSitBu2N(LiTHF2)SitBu2F的单体晶化，以含有四元环的二聚体(16)从正己烷中晶化(FuSitBu2NSitBu2LiF)2(17)。已确定了4、10、16、17的晶体结构。
• High-yield electrosynthesis of furylchlorosilanes, silyl and silanylene furans
  作者：Carole Moreau、Françoise Serein-Spirau、Michel Bordeau、Claude Biran

  DOI：10.1016/s0022-328x(98)00853-5

  日期：1998.11

  The intensiostatic sacrificial anode technique proved to be efficient for the silylation of 2-bromo- and 2,5-dibromofurans with trimethylchlorosilane and diorganodichlorosilanes with high selectivity and versatility not accessible by pure chemical routes. Furylsilanes, bromofurylsilanes, bis(furyl)silanes, bis(bromofuryl)silanes, furylchlorosilanes, bis(silyl and chlorosilyl)furans, poly[(silanylene)furylene] oligomers and [1(4)]dimethylsila-2,5-furanocalixarene were obtained in good to high yields. (C) 1998 Elsevier Science S.A. All rights reserved.
• Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair
  作者：Weidi Cao、Davin Tan、Richmond Lee、Choon-Hong Tan

  DOI：10.1021/jacs.7b13056

  日期：2018.2.7

  bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary

  报道了高度对映选择性双胍催化的酰基硅烷串联重排。通过在硅上添加氟化物来活化酰基硅烷以形成五配位阴离子硅酸盐中间体。然后硅酸盐经历烷基或芳基从硅原子迁移到相邻的羰基碳原子（1,2-阴离子重排），然后进行 [1,2]-布鲁克重排，以高产率提供具有优异对映选择性的仲醇（高达 95% ee）。α-甲硅烷基甲醇中间体的分离以及 DFT 计算表明，1,2-阴离子重排是通过双胍硅酸盐离子对发生的，这是立体确定步骤。然后通过随后的 [1,2]-布鲁克重排保留形成的手性中心而不发生反转。巴豆酰基硅烷顺利转化为高烯丙基线性巴豆醇，保留 E/Z 几何结构，未检测到支链醇。这清楚地表明 1,2-阴离子重排是通过三元而不是五元过渡态发生的。
• Intramolecular Diels-Alder reactions of furans with a merely strain-activated tetrasubstituted alkene: Bicyclopropylidene
  作者：Thomas Heiner、Sergei I. Kozhushkov、Mathias Noltemeyer、Thomas Haumann、Roland Boese、Armin de Meijere

  DOI：10.1016/0040-4020(96)00720-x

  日期：1996.9

  Bicyclopropylidene derivatives 1, 6, 8 with furan moieties attached on tethers of various length and nature all undergo clean intramolecular Diels-Alder reactions with complete endo-diastereoselectivities when heated to 70 - 130 degrees C, under 10 kbar pressure. The reaction rates are at]east as high or higher than those of analogously tethered methylenecyclopropane-furan derivatives 15, 17, 20, in spite of the fact that the reactive double bond in bicyclopropylidene is tetrasubstituted and not activated by any electron withdrawing group. Copyright (C) 1996 Elsevier Science Ltd