1-<(trimethylsilyl)oxy>-1-methoxy-1,3-butadiene | 110362-30-6

• 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: 1-<(trimethylsilyl)oxy>-1-methoxy-1,3-butadiene
• 英文别名: (Z)-((1-methoxybuta-1,3-dien-1-yl)oxy)trimethylsilane；(Z)-[(1-methoxybuta-1,3-dien-1-yl)oxy]trimethylsilane；(Z)-((1-methoxy-1,3-vinylene)oxy)trimethylsilane；1-methoxy-1-(trimethylsiloxy)-1,3-butadiene；1-methoxy-1-trimethylsilyloxybuta-1,3-diene；1-methoxy-1-trimethylsiloxybuta-1,3-diene；[(1Z)-1-methoxybuta-1,3-dienoxy]-trimethylsilane
• CAS: 110362-30-6
• 化学式: C₈H₁₆O₂Si
• 分子量: 172.299
• InChiKey: NOKYWNGQHBWZAP-FPLPWBNLSA-N

物化性质

• 沸点：
  163.4±23.0 °C(Predicted)
• 密度：
  0.872±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.51
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-<(trimethylsilyl)oxy>-1-methoxy-1,3-butadiene 在 zinc(II) chloride 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 24.33h， 生成 methyl 2-(N-benzylamino)-3-butenoate
  参考文献：
  名称：

  Regiochemical control in the preparation of 2-(nosyloxy) .beta.,.gamma.-unsaturated esters and 4-(nosyloxy) .alpha.,.beta.-unsaturated esters from 1-[(trimethylsilyl)oxy]-1-alkoxy 1,3-dienes

  摘要：

  A series of 1-[(trialkylsilyl)oxy]-1-alkoxy 1,3-dienes 1a-i were found to react with p-nitrobenzenesulfonyl peroxide in the presence of sodium methoxide or zinc chloride to give alkyl 2-[[(p-nitrophenyl)sulfonyl]oxy] beta-gamma-unsaturated esters 3 and alkyl 4-[[(p-nitrophenyl)sulfonyl]oxy] alpha,beta-unsaturated esters 4 which are readily separable. The regioselectivity is determined by kinetic versus thermodynamic control. When positions 2 or 4 of the diene are unsubstituted, the 2-isomer is the major product and is the kinetically fastest formed product. It can be thermally rearranged to the more stable 4-isomer. When alkyl substituents are present at either the 2- or 4-positions, only the 4-isomer is obtained. Substitution for nosylate by amine nucleophiles occurs by an S(N)2 process. Thus 2-amino beta,gamma-unsaturated esters and 4-amino alpha,beta-unsaturated esters can be prepared from the appropriate starting nosylate.

  DOI：

  10.1021/jo00003a022
• 作为产物：
  描述：

  三甲基氯硅烷 、 (Z)-methyl but-2-enoate 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以75%的产率得到1-<(trimethylsilyl)oxy>-1-methoxy-1,3-butadiene
  参考文献：
  名称：

  一种合成天然产物Tarchonanthuslactone异构 体的方法

  摘要：

  本发明提供了一种合成天然产物Tarchonanthuslactone异构体的方法，以三羟基丁酸甲酯为原料，经过PMB酯保护，LiAlH4还原，Swern氧化，Mukaiyama Aldol反应，酯水解，Yanaguchi关环，去保护，缩合得到天然产物Tarchonanthuslactone的异构体。本发明的合成路线设计新颖合理，原料价廉易得，操作工艺简便，反应条件温和，速率快，副反应相对少，操作简便，原料廉价易得，可大大降低合成成本。

  公开号：

  CN104402852B

文献信息

• Stereoselective total synthesis of (–)-(6<i>S</i>,2′<i>R</i>)-cryptocaryalactone
  作者：Feifei Huang、Xiaotong Li、Shuangjie Lin、Cheng Liang、Shuangping Huang、Xiaoji Wang

  DOI：10.1080/14786419.2017.1312392

  日期：2017.10.18

  We described a novel stereoselective total synthesis of (–)-(6S,2′R)-cryptocaryalactone, a natural product containing syn/anti-6,8-diol/5,6-dihydro-2H-pyran-2-one unit. The approach, which characterised a highly diastereoselective chelation-controlled Mukaiyama aldol reaction of a benzyl-protected aldehyde and a Yamaguchi lactonisation of a δ-hydroxy-trans-α,β-unsaturated carboxylic acid, is an alternative

  我们描述了一种新型的立体选择性全合成（-）-（6S，2'R）-隐乳内酯，这是一种天然产物，其中含有syn / anti -6,8-diol / 5,6-dihydro-2 H -pyran-2-one单元。该方法的特征是苄基保护的醛的高度非对映选择性螯合控制的Mukaiyama aldol反应和δ-羟基反式-α，β-不饱和羧酸的Yamaguchi内酯化，是一种针对隐甲酰内酯的替代合成策略。
• Synthesis of Homophthalates from Allenic Diesters: Conversion into Viocristin and Analogues, and Application to 6-Methylpretetramid.
  作者：Donald W. Cameron、Ece Caliskan、Peter G. Griffiths

  DOI：10.1071/ch99065

  日期：——

  Oxy-substituted homophthalic anhydrides have been synthesized by cycloaddition of di- and tri-oxy butadienes to the allenic diester (1). By base-catalysed cycloaddition to appropriate benzoquinones they have afforded new syntheses of viocristin (19), isoviocristin (20) and analogous 1,4-anthraquinones. Related chemistry has led to the naphthalene (34) and the anhydride (35), intermediates in published syntheses of semivioxanthin and 6- methylpretetramid respectively.

  氧代均苯二甲酸酐是通过二氧和三氧丁二烯与异链二酯（1）的环加成反应合成的。 将二氧基和三氧基丁二烯环加成均苯二甲酸酯 (1)。通过碱催化 通过与适当的苯醌进行环加成，他们合成了新的 viocristin (19)、isoviocristin (20) 和类似的 1,4-anthraquinones 的新合成。相关的 萘（34）和酐（35）、 的中间体。 萘 (34) 和酸酐 (35)，它们分别是已发表的半二氧杂蒽和 6-甲基维甲酸合成的中间体。
• Asymmetric vinylogous Mukaiyama aldol reaction of isatins under bifunctional organocatalysis: enantioselective synthesis of substituted 3-hydroxy-2-oxindoles
  作者：Víctor Laina-Martín、Jorge Humbrías-Martín、José A. Fernández-Salas、José Alemán

  DOI：10.1039/c8cc00759d

  日期：——

  A highly enantioselective organocatalytic vinylogous Mukaiyama aldol reaction of silyloxy dienes and isatins under bifunctional organocatalysis is presented. Substituted 3-hydroxy-2-oxindoles are synthesised in good yields and enantioselectivities. These synthetic intermediates are used for the construction of more complex molecules with biological properties such as the formal synthesis of a CB2 agonist

  提出了在双功能有机催化下，甲硅烷氧基二烯和异丁烯类具有高度对映选择性的有机催化乙烯基Mukaiyama aldol反应。以高产率和对映选择性合成取代的3-羟基-2-氧吲哚。这些合成中间体用于构建具有生物学特性的复杂分子，例如所提出的CB2激动剂的正式合成。
• Reaction of Bromonaphthofurans with Bis(pinacolato)diboron.
  作者：Margaret A. Brimble、Fatiah Issa

  DOI：10.1071/ch99073

  日期：——

  The synthesis of a dimeric pyranonaphthoquinone (8) was investigated focusing on a late-stage biaryl coupling of suitably functionalized bromonaphthofurans by using Suzuki–Miyaura methodology. Bromonaphthofuran (16) underwent reaction with bis(pinacolato)diboron in the presence of PdCl2(dppf) to afford boronate ester (21) and furonaphthofuran (22). ‘In situ’coupling of the boronate ester (21) with aryl bromide (16) to the desired dimer (11) was not realized. Bromonaphthofuran (17), prepared by Diels–Alder/retro-Claisen reaction of bromonaphthoquinone (24) with diene (25), underwent Suzuki–Miyaura coupling to naphthofuran (27) and boronate ester (28). Numerous attempts to alter the reaction conditions to effect homocoupling of bromide (17) to biaryl (19) were unsuccessful. Bromopyranonaphthoquinone (18) prepared by oxidative rearrangement of (17) failed to undergo Suzuki–Miyaura coupling.

  研究了二聚吡喃萘醌（8）的合成，重点是 的后期双芳基偶联。 通过使用 Suzuki-Miyaura 方法。溴萘并呋喃 (16) 与双(频哪醇) 与双(频哪醇)二硼在 PdCl2（dppf）存在下发生反应。 PdCl2(dppf) 的存在下与双(频哪醇)二硼发生反应，生成硼酸酯 (21) 和 呋喃（22）。硼酸酯 硼酸酯 (21) 与芳基溴化物 (16) 的 "原位 "偶联生成所需的二聚体 (11)。 没有实现。溴代萘呋喃（17）的制备方法是 溴萘醌（24）与二烯（25）的 Diels-Alder/retro-Claisen 反应制备溴萘呋喃（17）。 二烯 (25) 发生 Diels-Alder/retro-Claisen 反应制备的溴萘醌 (17)，经 Suzuki-Miyaura 偶联生成萘呋喃 (27) 和 硼酸酯 (28)。为了改变反应条件以实现溴呋喃的同偶联反应，人们进行了无数次尝试。 溴（17）与双芳基（19）的同偶联反应，但都没有成功。 通过 (17) 的氧化重排制备的溴吡喃萘醌 (18) 未能发生铃木-宫浦偶联反应。
• Chiral N,N′-dioxide–In(OTf)₃-catalyzed asymmetric vinylogous Mukaiyama aldol reactions
  作者：Kai Fu、Jianfeng Zheng、Lili Lin、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c4cc09820j

  日期：——

  Chiral N,N'-dioxide-In(OTf)3 complexes were developed as efficient catalysts to catalyze the vinylogous Mukaiyama aldol reaction of the silyl dienol ester with aldehydes. The corresponding delta-hydroxy-alpha,beta-unsaturated esters were obtained in up to 99% yield and 98% ee. Moreover, the obtained (R)-3v can be easily transformed to natural bioactive products.

  已开发出手性N，N'-二氧化物-In（OTf）3配合物，作为催化甲硅烷基二烯醇酯与醛类的乙烯基Mukaiyama aldol反应的有效催化剂。以高达99％的收率和98％的ee获得相应的δ-羟基-α，β-不饱和酯。而且，所获得的（R）-3v可以容易地转化为天然生物活性产物。