carbonic acid 1,1-dimethylethyl (2E)-1-methyl-2-butenyl ester | 369391-26-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: carbonic acid 1,1-dimethylethyl (2E)-1-methyl-2-butenyl ester
• 英文别名: tert-butyl 1-methyl-but-2-enyl carbonate；(E)-tert-butyl pent-3-en-2-yl carbonate；tert-butyl [(E)-pent-3-en-2-yl] carbonate
• CAS: 369391-26-4
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: LLDJQVLEGYGVIP-VOTSOKGWSA-N

物化性质

• 沸点：
  208.9±19.0 °C(Predicted)
• 密度：
  0.943±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-硝基丙烷 、 carbonic acid 1,1-dimethylethyl (2E)-1-methyl-2-butenyl ester 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二甲基亚砜 为溶剂， 反应 48.0h， 以41%的产率得到(E)-4,5-dimethyl-5-nitrohex-2-ene
  参考文献：
  名称：

  钯催化仲硝基烷烃的烯丙基烷基化

  摘要：

  利用催化量的外部碱，开发了钯催化仲硝基烷烃的烯丙基烷基化反应。简单的碳酸烯丙酯和单取代的碳酸烯丙酯用作亲电子试剂，大体积的仲硝基烷烃用作亲核试剂。这是庞大的仲硝基烷烃（例如2-硝基庚烷）的第一个催化烯丙基烷基化反应。在非质子极性溶剂DMSO中使用强碱DBU是实现高反应活性的关键。为了发展不对称反应，2-芳基恶唑啉配体PHOX L1在诱导π-烯丙基部分的手性方面给出了极好的结果。至于在NO 2官能团的α位上的不对称诱导，含游离OH-基团的2-芳基恶唑啉配体L4 表现出中等选择性。

  DOI：

  10.1016/j.tet.2007.03.062
• 作为产物：
  描述：

  3-penten-2-ol 、 二碳酸二叔丁酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 carbonic acid 1,1-dimethylethyl (2E)-1-methyl-2-butenyl ester
  参考文献：
  名称：

  钴或钯催化氮杂芳基甲基胺的烯丙基取代合成高烯丙胺

  摘要：

  描述了 Pd(OAc) 2 /Nixantphos 或 CoI 2 /Nixantphos 催化的氮杂芳基甲基胺的弱酸性 C(sp) 3 –H 键的烯丙基取代。该方法有利于获得各种含有高烯丙胺的杂芳环（39 个例子，产率 30-98%），具有优异的官能团耐受性和非对映选择性。与Pd/Nixantphos配合物相比，Co/Nixantphos催化可以获得具有良好至优异非对映选择性的环状产物。重要的是，CoI 2 /( R,R )-Me-Duphos 催化反应表现出中等的对映选择性。此外，这种转变的可扩展性也得到了成功的证明。

  DOI：

  10.1021/acs.orglett.4c00551

文献信息

• General Method for the Palladium-Catalyzed Allylation of Aliphatic Alcohols
  作者：Anthony R. Haight、Eric J. Stoner、Matthew J. Peterson、Vandana K. Grover

  DOI：10.1021/jo0301907

  日期：2003.10.1

  A palladium catalysis-mediated approach to coupling aliphatic alcohols with allyl carbonates has been developed. The method allows for the allylation of primary, secondary, and tertiary alcohols efficiently under mild conditions. Limitations were explored as well as the asymmetric application of the chemistry. Regiochemical and olefin geometry was controlled in the coupling of unsymmetrical allylating

  已经开发了钯催化介导的将脂肪族醇与碳酸烯丙酯偶联的方法。该方法允许在温和条件下有效地使伯，仲和叔醇烯丙基化。探索了局限性以及化学的不对称应用。在不对称烯丙基化剂的偶联中控制区域化学和烯烃的几何形状。在偶合中观察到瞬态碳酸烯丙酯，其包括碳酸烯丙酯与必要的醇的反羧化。
• Contemporaneous Dual Catalysis by Coupling Highly Transient Nucleophilic and Electrophilic Intermediates Generated in Situ
  作者：Barry M. Trost、Xinjun Luan

  DOI：10.1021/ja110501v

  日期：2011.2.16

  contemporaneous dual catalysis, that selectively couples two highly reactive catalytic intermediates while overcoming competing trapping by stoichiometric reactive species also present in the reaction. The reaction proceeds via the convergence of a vanadium-catalyzed propargylic rearrangement and a palladium-catalyzed allylic alkylation. It generates a variety of α-allylated α,β-unsaturated ketones, which are

  我们在此报告了一种新的过程，我们称之为同期双催化，它选择性地偶联两种高活性催化中间体，同时克服反应中也存在的化学计量活性物质的竞争性捕获。该反应通过钒催化的炔丙基重排和钯催化的烯丙基烷基化的收敛进行。它会生成多种 α-烯丙基化的 α,β-不饱和酮，这些酮不容易通过其他方式获得。值得注意的是，这种双重催化是通过使用低催化剂负载量（1.0 mol % [Pd]，1.5 mol % [V]）实现的，并提供了良好至极好的收率（高达 98%）的所需产物。
• Simple phosphinite–oxazoline ligands for asymmetric catalysis
  作者：Geraint Jones、Christopher J Richards

  DOI：10.1016/s0040-4039(01)01041-3

  日期：2001.8

  4-(Hydroxymethyl)oxazolines, derived from (S)-serine methyl ester and a variety of acid chlorides (RCOCl), were reacted with Ph2PCl to give new phosphinite-oxazoline P-N ligands. These mediate the palladium catalysed asymmetric alkylation with dimethyl malonate with the following racemic propenyl substrates (RCH)-C-1=CHCH(OX)R-1: (a) R-1 =Ph, X = Ac-96% e.e.(S) with R=Ph; (b) R-1 = Me, X = CO2' Bu-70% e.e.(S) with R=(eta (5)-C5H4)(eta (4)-C4Ph4)CO. (C) 2001 Published by Elsevier Science Ltd.
• A Diosphenol-Based Strategy for the Total Synthesis of (−)-Terpestacin
  作者：Barry M. Trost、Guangbin Dong、Jennifer A. Vance

  DOI：10.1021/ja070571s

  日期：2007.4.1

  A novel diosphenol-based strategy has been developed for the enantioselective synthesis of (-)-terpestacin by multiple usage of the alpha-diketone functionality, first in the "Pd AAA-Claisen rearrangement" protocol, and second by the employment of its oxidized form, the ene-1,2-dione, as an excellent Michael acceptor. This synthesis demonstrates that the sequence of O-allylation-Claisen rearrangement provides a chemo- and regioselective enolate allylation, which can be performed asymmetrically with respect to the enolate or allyl fragment or both. In addition, many interesting chemoselectivity issues, including a highly selective RCM and a dihydroxylation, have been addressed. Overall, this synthesis was accomplished in 20 longest linear steps (24 total steps) from the inexpensive and commercially available 3-methyl-1,2-cyclopentanedione.
• Pd-Catalyzed allylic alkylation of secondary nitroalkanes
  作者：Keisuke Maki、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2007.03.062

  日期：2007.5

  A Pd-catalyzed allylic alkylation of secondary nitroalkanes, using a catalytic amount of external base, was developed. Simple allyl carbonate and monosubstituted allyl carbonates were used as electrophiles, and bulky secondary nitroalkanes were used as nucleophiles. This is the first catalytic allylic alkylation of bulky secondary nitroalkanes, such as 2-nitroheptane. The use of the strong base DBU

  利用催化量的外部碱，开发了钯催化仲硝基烷烃的烯丙基烷基化反应。简单的碳酸烯丙酯和单取代的碳酸烯丙酯用作亲电子试剂，大体积的仲硝基烷烃用作亲核试剂。这是庞大的仲硝基烷烃（例如2-硝基庚烷）的第一个催化烯丙基烷基化反应。在非质子极性溶剂DMSO中使用强碱DBU是实现高反应活性的关键。为了发展不对称反应，2-芳基恶唑啉配体PHOX L1在诱导π-烯丙基部分的手性方面给出了极好的结果。至于在NO 2官能团的α位上的不对称诱导，含游离OH-基团的2-芳基恶唑啉配体L4 表现出中等选择性。