tert-butyldimethyl<((E)-3-phenyl-1-propenyl)oxy>silane | 135457-36-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyldimethyl<((E)-3-phenyl-1-propenyl)oxy>silane
• 英文别名: 1-tert-butyldimethylsilyloxy-3-phenylpropene；tert-butyl-dimethyl-(3-phenylprop-1-enoxy)silane
• CAS: 135457-36-2
• 化学式: C₁₅H₂₄OSi
• 分子量: 248.44
• InChiKey: SKAGNXXTRKOWKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  tert-butyldimethyl<((E)-3-phenyl-1-propenyl)oxy>silane 在 溴 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以13%的产率得到2-bromo-1-tert-butyldimethylsilyloxy-3-phenylpropene
  参考文献：
  名称：

  合成 2,2-[60] 富勒烯的一般方法：[60] 富勒烯与 2-溴烯醇甲硅烷基醚的反应

  摘要：

  通过氟离子介导的 [60] 富勒烯与 2-溴烯醇甲硅烷基醚的反应合成了五种 2,2-[60] 富勒烯烷醛，该反应很容易通过相应烯醇甲硅烷基醚的 2-溴化制备。反应性显着不同，这取决于 2-溴烯醇甲硅烷基醚的稳定性。2-溴烯醇三甲基甲硅烷基醚在温和条件下（KF/18-crown-6-ether）的反应实现了高产率和选择性。另一方面，稳定的 2-溴烯醇叔丁基二甲基甲硅烷基醚的反应需要使用更具反应性的四丁基氟化铵作为氟离子源。

  DOI：

  10.1055/s-0030-1258112
• 作为产物：
  描述：

  苯丙醛 、 叔丁基二甲基氯硅烷 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 以33 %的产率得到tert-butyldimethyl<((E)-3-phenyl-1-propenyl)oxy>silane
  参考文献：
  名称：

  2-吡喃酮和无环烯醇醚之间的非对映和对映选择性逆电子需求狄尔斯-阿尔德环加成

  摘要：

  研究了 2-吡喃酮和无环烯醇醚之间的反电子需求狄尔斯-阿尔德环加成反应。以非对映选择性和对映选择性获得桥联双环内酯，并将其转化为合成相关的多取代对映富集环己烯和环己二烯衍生物。机制证据以及 DFT 计算都指向逐步机制。

  DOI：

  10.1002/anie.202208185

文献信息

• Chiral Allenes via Alkynylogous Mukaiyama Aldol Reaction
  作者：Aurélien Tap、Aurélie Blond、Vijay N. Wakchaure、Benjamin List

  DOI：10.1002/anie.201603649

  日期：2016.7.25

  development of a catalytic enantioselective alkynylogous Mukaiyama aldol reaction. The reaction is catalyzed by a newly designed chiral disulfonimide and delivers chiral allenoates in high yields and with excellent regio‐, diastereo‐, and enantioselectivity. Our process tolerates a broad range of aldehydes in combination with diverse alkynyl‐substituted ketene acetals. The reaction products can be readily

  在本文中，我们描述了催化对映选择性炔烃Mukaiyama醛醇缩合反应的发展。该反应由新设计的手性二磺酰亚胺催化，并以高收率和极佳的区域，非对映和对映选择性提供手性烯丙酸酯。与多种炔基取代的乙烯酮缩醛组合使用，我们的方法可耐受多种醛类。反应产物可以容易地衍生以提供各种高度取代的对映体富集的结构单元。
• Photoredox-Catalyzed Generation of Acetonyl Radical in Flow: Theoretical Investigation and Synthetic Applications
  作者：Manuel Anselmo、Andrea Basso、Stefano Protti、Davide Ravelli

  DOI：10.1021/acscatal.8b03875

  日期：2019.3.1

  A hydrogen atom transfer (HAT) step from acetone allowed the smooth generation of acetonyl radical that was then exploited as synthon in the mild formation of C–C bonds under flow conditions. The process was promoted by aryl radicals photocatalytically generated via single-electron transfer (SET) reduction of arenediazonium salts. The mechanism has been investigated by a combined experimental and computational

  丙酮中的氢原子转移（HAT）步骤使丙酮基自由基得以顺畅生成，然后该丙酮基自由基在流动条件下以温和方式形成C–C键时被用作合成子。该过程是通过芳族氮杂鎓盐的单电子转移（SET）还原通过光催化产生的芳基来促进的。该机理已通过组合的实验和计算方法进行了研究，并得到了氘标记实验的进一步支持。
• Catalyst-controlled diastereoselectivity reversal in the formation of dihydropyrans
  作者：Taichi Kano、Hiroki Maruyama、Chihiro Homma、Keiji Maruoka

  DOI：10.1039/c8cc01443d

  日期：——

  An enantioselective synthesis of cis-dihydropyrans as the formal HDA reaction products was achieved through the catalyst-controlled anti-selective conjugate addition of aldehydes to β,γ-unsaturated α-keto esters. The observed unusual cis-selectivity could be attributed to the stabilization of the less favorable transition state for anti-conjugate adducts by the hydrogen bonding between the hydroxy

  通过醛控制的反选择性共轭醛加成到β，γ-不饱和α-酮酯中，可以实现顺式-二氢吡喃类化合物作为对映体HDA反应产物的对映选择性合成。观察到的异常的顺式选择性归因于氨基二醇催化剂的羟基与β，γ-不饱和α-酮酯之间的氢键，使抗共轭加合物的较不利的过渡态稳定。
• A practical reversed-polarity alternative to organocuprate conjugate addition chemistry. Halocarbon coupling reactions of enal- and enone-derived allylnickel reagents
  作者：John R. Johnson、Paul S. Tully、Peter B. Mackenzie、Michal Sabat

  DOI：10.1021/ja00016a037

  日期：1991.7

  A direct method for the conversion of conjugated enals and enones into [1-[(trialkylsilyl)oxy]allyl]nickel(II) chloride complexes is described. Reaction of R1CH = CR2CHO (R1 = H, Me, Ph; R2 = H and R1 = H; R2 = Me) with Ni(COD)2 (COD = 1,5-cyclooctadiene) and ClSiMe2R3 (R3 = Me or t-Bu) affords bis[[1,2,3-eta-3-1-[(trialkylsilyl)oxy]-2-propenyl](mu-chloro)nickel(II)] complexes 1a-f as burgundy-red crystalline solids in high to excellent yields (86-98%). The X-ray crystal structure of 1c confirms the eta-3-bonding mode for the allyl ligand and provides evidence of significant overlap of oxygen lone pair electron density with the allyl pi-system. Reaction of 3-buten-2-one with Ni(COD)2 and Me3SiCl similarly affords bis[[1,2,3-eta-3-1-methyl-1-[(trimethylsilyl)oxy]-2-propenyl](mu-chloro)nickel(II)] (1g) in 72% yield, while the corresponding 2-cyclopentenone reaction fails, giving rise to a nickel metal mirror. The latter reaction does, however, succeed when conducted in the presence of pyridine, giving bis(pyridine)(chloro)[1,2,3-eta-3-1-[(tert-butyldimethylsilyl)oxy]-2-cyclopentenyl]nickel(II) complex (1h) in 95% yield. Irradiation of 1e (R1 = R2 = H; R3 = t-Bu) in the presence of 2-iodopropane affords tert-butyldimethylsilyl (E)-enol ether 2a in 78% yield (E:Z = 10:1). Similar results are observed with [1-(trialkylsilyl)oxy]allyl]nickel(II) chloride complexes generated in situ from propenal, 2-methylpropenal, 2-butenal, 2-methyl-2-butenal, hexenal, and 3-buten-2-one, in coupling reactions with 1-iodobutane, 2-iodopropane, 1-bromoethene, 2-bromopropene, bromobenzene, o-bromobenzaldehyde, and isobutyryl chloride, affording the corresponding silyl (E)-enol ethers in 60-78% isolated, purified yield, based on Ni(1,5-COD)2. High C(3) regioselectivities (> 20:1) are observed for all of the C(3)-unsubstituted enals, while lower regioselectivities, in the range of 4-6:1 before purification, are observed for the C(3)-substituted enals; regioisomerically pure materials are obtained upon chromatography. Moderate to high E:Z stereoselectivities (E:Z = 4-15:1 before purification; E:Z = 20-50:1 after chromatography) are observed in all cases, save the reaction of isobutyryl chloride with 1e and the reaction of the 3-buten-2-one-derived allylnickel complex with 2-bromopropene, both of which give 1:1 E:Z ratios. In a more convenient, economical, and general variant, Ni(COD)2 is generated in situ via the sodium metal reduction of NiCl2(pyridine)4 (in turn prepared from NiCl2(H2O)6) in the presence of cyclooctadiene and reacted with the enal or enone in the presence of ClSiMe2R3 to afford the [1-[(trialkylsilyl)oxy]allyl](chloro)(pyridine)nickel(II) complex, which is treated with the halocarbon and irradiated to afford the usual silyl enol ether products. Yields of 63-84%, based on enal or enone, were observed in reactions with propenal, (E)-2-hexenal, 2-cyclopentenone, and 2-cyclohexenone in reactions with bromoethene, bromobenzene, and 1-iodobutane using this procedure.