3-iodopropyl pivalate | 139527-21-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-iodopropyl pivalate
• 英文别名: 3-Iodopropyl 2,2-dimethylpropanoate
• CAS: 139527-21-2
• 化学式: C₈H₁₅IO₂
• 分子量: 270.11
• InChiKey: XRSFUTVIRMMALA-UHFFFAOYSA-N

物化性质

• 沸点：
  245.1±23.0 °C(Predicted)
• 密度：
  1.476±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-iodopropyl pivalate 在 氢碘酸 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 18.0h， 生成 (S)-(-)-3-(Benzyloxy)-6-pivaloxy-1-hexene
  参考文献：
  名称：

  Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes

  摘要：

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

  DOI：

  10.1021/jo00094a027
• 作为产物：
  描述：

  pivalic acid-(3-chloro-propyl ester) 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 3-iodopropyl pivalate
  参考文献：
  名称：

  Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes

  摘要：

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

  DOI：

  10.1021/jo00094a027

文献信息

• Fe(II)-Catalyzed Amination of Aromatic C−H Bonds via Ring Opening of 2<i>H</i>-Azirines: Synthesis of 2,3-Disubstituted Indoles
  作者：Samaresh Jana、Mack D. Clements、Barry K. Sharp、Nan Zheng

  DOI：10.1021/ol101130e

  日期：2010.9.3

  A general method for the synthesis of 2,3-disubstituted indoles is described. The key feature of this method is the amination of aromatic C−H bonds via FeCl2-catalyzed ring opening of 2H-azirines. The method tolerates a variety of functional groups such as Br, F, NO2, OMe, CF3, OTBS, alkenes, and OPiv. The method can also be extended to synthesize azaindoles.

  描述了合成 2,3-二取代吲哚的一般方法。该方法的主要特征是通过 FeCl 2催化的 2 H -氮杂环开环使芳香族 CH 键胺化。该方法耐受多种官能团，例如 Br、F、NO 2、OMe、CF 3、OTBS、烯烃和 OPiv。该方法还可以扩展到合成氮杂吲哚。
• Neopentyl and Neophyl Groups: New Nontransferable Groups for Organocopper and Organozinc Chemistry
  作者：Christian Lutz、Philip Jones、Paul Knochel

  DOI：10.1055/s-1999-3387

  日期：1999.2

  Neopentyl and Neophyl groups have been found to be excellent nontransferable groups for organozinc and organocopper chemistry. We have shown that mixed diorganozincs of the type FG-R-Zn(CH2CMe2R) can be used advantageously for the enantioselective addition to aldehydes. These mixed copper or zinc reagents are also found to be very efficient in the Michael addition to various activated alkenes.

  研究发现，新戊基和新苯基是一类优良的非转移性基团，适用于有机锌和有机铜化学。我们已经证明，类型为 FG-R-Zn(CH2CMe2R) 的混合二有机锌可以用于对醛的对映选择性加成。这些混合铜或锌试剂在向各种活化烯烃的迈克尔加成中也表现出非常高的效率。
• Enantioselective preparation of polyfunctional secondary allylic alcohols using functionalized dialkylzincs prepared by a copper(I) catalyzed iodine-zinc exchange reaction.
  作者：Michael J. Rozema、Christina Eisenberg、Henning Lütjens、Roswitha Ostwald、Kevin Belyk、Paul Knochell

  DOI：10.1016/s0040-4039(00)93393-8

  日期：1993.5

  exchange reaction leading to polyfunctional dialkylzincs. The catalytic asymmetric addition of these zinc reagents to a wide range of α,β-unsaturated aldehydes provides polyfunctional allylic alcohols with a high enantioselectivity.

  催化量的Cu（I）盐极大地促进了碘-锌交换反应，从而形成了多官能的二烷基锌。将这些锌试剂催化不对称地添加到各种α，β-不饱和醛中，可提供具有高对映选择性的多官能烯丙基醇。
• Preparation of polyfunctional ketones by a cobalt(II) mediated carbonylation of organozinc reagents
  作者：A. Devasagayaraj、P. Knochel

  DOI：10.1016/0040-4039(95)01802-o

  日期：1995.11

  Functionalized organozinc halides can be efficiently carbonylated under atmospheric pressure in the presence of cobalt(II) bromide in THF:NMP leading to polyfunctional symmetrical ketones in 56–80 % yield.

  在溴化钴（II）在THF：NMP中的存在下，官能化的有机锌卤化物可以在大气压下有效地羰基化，从而产生多官能对称的酮，产率为56-80％。
• Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes
  作者：Jixin Wang、Zhili Duan、Xingchen Liu、Shoucheng Dong、Kaixin Chen、Jie Li

  DOI：10.1002/anie.202202379

  日期：2022.4.19

  solid silylzinc pivalate prepared from the silyllithium reagents via transmetalation with Zn(OPiv)2 is reported. These silylzinc pivalates showed enhanced air and moisture stability and unique reactivity in the nickel-catalyzed regioselective alkyl and benzylsilylation of alkenes. Kinetic experiments highlighted the crucial involvement of OPiv-coordination in improving the reactivity of silylzinc pivalates

  报道了一种由甲硅烷基锂试剂通过与Zn(OPiv) 2的金属转移反应制备的新型盐稳定固体新戊酸甲硅烷基锌。这些新戊酸甲硅烷基锌在镍催化的烯烃区域选择性烷基化和苄基甲硅烷基化中表现出增强的空气和水分稳定性以及独特的反应性。动力学实验强调了 OPiv 配位在提高新戊酸甲硅烷基锌反应性方面的关键作用。