tert-butyl(((E)-1-methoxybuta-1,3-dien-1-yl)oxy)dimethylsilane | 107174-33-4

• 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: tert-butyl(((E)-1-methoxybuta-1,3-dien-1-yl)oxy)dimethylsilane
• 英文别名: 1-(tert-butyldimethylsilyl)-1-methoxybutadiene；tert-butyl-[(1E)-1-methoxybuta-1,3-dienoxy]-dimethylsilane
• CAS: 107174-33-4
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: AYUCMORHKFSWMF-MDZDMXLPSA-N

物化性质

• 沸点：
  218.2±23.0 °C(predicted)
• 密度：
  0.867±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  3-苄氧基丙醛 、 tert-butyl(((E)-1-methoxybuta-1,3-dien-1-yl)oxy)dimethylsilane 在 盐酸 、 丁腈 、 二氯苯酚溴酯 、 potassium tert-butylate 、 N-(p-toluenesulfonyl)-(S)-tryptophan 作用下， 以 四氢呋喃 、 二氯甲烷 、 异丙醇 为溶剂， 生成 methyl 2-{(2S,4S,6S)-6-[2-(benzyloxy)ethyl]-2-phenyl-1,3-dioxan-4-yl}acetate
  参考文献：
  名称：

  用于目标捕鱼的阿托伐他汀内酯接头结构的合成

  摘要：

  为了将阿托伐他汀内酯 9 连接到用于基于亲和力的目标捕鱼的链接器，开发了一条通往吡咯羧酸 8 的简洁路线。合成含二醇侧链的关键特征是催化对映选择性乙烯基羟醛反应，产生 5-羟基烯酸酯 14 (88% ee)。随后的分子内 oxa-Michael 加成和酰胺还原提供了关键的构件 5。 正如我们之前所描述的，胺 5 与二酮 6 的 Paal-Knorr 反应产生吡咯 7，后者在羧化后提供酸 8。由于阿托伐他汀内酯是一种作为酸 7 的苯胺衍生物，我们制备了两个具有苯胺末端的接头。为此目的，基于乙二醇的烯丙基醚20和27通过交叉复分解与硝基苯乙烯22组合。硝基和双键氢化后，分别得到苯胺25和29。苯胺与羧酸8缩合得到相应的酰胺30和35。侧链的加工然后分别提供阿托伐他汀内酯接头构建体34和39。

  DOI：

  10.1002/ejoc.201201154
• 作为产物：
  描述：

  巴豆酸甲酯 、 叔丁基二甲基氯硅烷 在 N,N-二甲基丙烯基脲 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以86%的产率得到tert-butyl(((E)-1-methoxybuta-1,3-dien-1-yl)oxy)dimethylsilane
  参考文献：
  名称：

  用于目标捕鱼的阿托伐他汀内酯接头结构的合成

  摘要：

  为了将阿托伐他汀内酯 9 连接到用于基于亲和力的目标捕鱼的链接器，开发了一条通往吡咯羧酸 8 的简洁路线。合成含二醇侧链的关键特征是催化对映选择性乙烯基羟醛反应，产生 5-羟基烯酸酯 14 (88% ee)。随后的分子内 oxa-Michael 加成和酰胺还原提供了关键的构件 5。 正如我们之前所描述的，胺 5 与二酮 6 的 Paal-Knorr 反应产生吡咯 7，后者在羧化后提供酸 8。由于阿托伐他汀内酯是一种作为酸 7 的苯胺衍生物，我们制备了两个具有苯胺末端的接头。为此目的，基于乙二醇的烯丙基醚20和27通过交叉复分解与硝基苯乙烯22组合。硝基和双键氢化后，分别得到苯胺25和29。苯胺与羧酸8缩合得到相应的酰胺30和35。侧链的加工然后分别提供阿托伐他汀内酯接头构建体34和39。

  DOI：

  10.1002/ejoc.201201154

文献信息

• Concise approach to the aromatic yohimboid and protoberberine alkaloids via intramolecular Diels-Alder reactions
  作者：Stephen F. Martin、Leo S. Geraci

  DOI：10.1016/s0040-4039(00)82439-9

  日期：——

  The aromatic yohimboid indole alkaloid oxogambirtannine (9) was synthesized in high yield via the intramolecular [4 + 2] cycloaddition/dehydrogenation of the substituted β-carboline 13, which was readily accessed by the reaction of 10 with the acid chloride 11 in the presence of the diene 12. In a similar manner the prototypical protoberberine skeleton 20 was rapidly constructed upon cyclization of

  通过取代的β-咔啉13的分子内[4 + 2]环加成/脱氢反应，高收率合成了芳香族育亨宾吲哚生物碱oxambiambirtannine（9），在存在的情况下10与酰基氯11的反应很容易获得。二烯12。以类似的方式，在取代异喹啉17环化后，快速构建原型小ber碱骨架20。
• Disulfonimide-Catalyzed Asymmetric Vinylogous and Bisvinylogous Mukaiyama Aldol Reactions
  作者：Lars Ratjen、Pilar García-García、Frank Lay、Michael Edmund Beck、Benjamin List

  DOI：10.1002/anie.201005954

  日期：2011.1.17

  talk about six! A new chiral disulfonimide catalyzed vinylogous Mukaiyama aldol addition of crotonic acid derived nucleophiles to aldehydes has been developed and the concept of vinylogy was further expanded to double vinylogous, sorbic acid derived nucleophiles. This reaction is an example of a previously unknown ε‐selective bisvinylogous Mukaiyama Aldol addition that extends the substrate by six

  让我们谈谈六个！已经开发了一种新的手性二磺酰亚胺催化的巴豆酸衍生的亲核试剂向醛的乙烯性Mukaiyama醛醇醛加成反应，并且乙烯基学的概念进一步扩展为双乙烯性，山梨酸衍生的亲核试剂。该反应是先前未知的ε-选择性双乙烯基长的Mukaiyama Aldol加成的一个例子，该加成作用将底物延伸了六个碳原子（请参见方案）。
• Unified strategy for synthesis of indole and 2-oxindole alkaloids
  作者：Stephen F. Martin、James E. Hunter、Brigitte Benage、Leo S. Geraci、Michael Mortimore

  DOI：10.1021/ja00016a036

  日期：1991.7

  A concise and general entry to representative indole alkaloids of the yohimboid, heteroyohimboid, corynantheoid, and 2-oxindole classes has been developed exploiting a strategy that features intramolecular Diels-Alder reactions for the facile construction of the D/E ring subunits of the target alkaloids. The efficacy of the approach is first illustrated by a two-step total synthesis of the yohimboid alkaloid oxogambirtannine (2) from 22. Thus, the Diels-Alder substrate 25, which was prepared by nucleophilic addition of vinyl ketene acetal 24 to the intermediate N-acyliminium salt formed in situ upon reaction of 22 with 23, was heated in the presence of benzoquinone to give a mixture of diastereoisomeric cycloadducts 26 and 27; these adducts underwent spontaneous oxidation to furnish 2. In another application of the strategy, the [4 + 2] heterocyclization of 34a, which was formed upon nucleophilic addition of 1-[(trimethylsilyl)oxy]butadiene to the N-acyliminium salt generated in situ upon treatment of 22 with crotonyl chloride, afforded a mixture (ca. 9:1) of cycloadducts 35a and 36a. The major adduct 35a was converted to 42a using a general procedure for effecting beta-carbomethoxylation of enol ethers to give vinylogous carbonates. Subsequent reduction of 42a to the heteroyohimboid alkaloids (+/-)-tetrahydroalstonine (3) and (+/-)-cathenamine (4) was achieved by selective delivery of 2 or 1 equiv of hydride, respectively. When 42a was treated with sodium amide, stereoselective beta-elimination ensued to give 49, which was converted by chemoselective hydride reduction into the corynantheoid alkaloid (+/-)-geissoschizine (5). Facile access to alkaloids of the 2-oxindole family was realized by using a new protocol for achieving stereoselective, oxidative rearrangements of beta-carboline N(b) lactams into 3,3-disubstituted 2-oxindoles. Thus, exposure of 42a to tert-butyl hypochlorite followed by acid and silver ion induced rearrangement of the intermediate 3-chloroindolenine gave 50, with only traces of the C(7) epimer being detected. Hydride reduction of 50 gave (+/-)-isopteropodine (6), acid-catalyzed isomerization of which furnished an equilibrium mixture (1:3) of 6 and (+/-)-pteropodine (51). The stereochemical course of the intramolecular hetero-Diels-Alder reaction of 34a to give 35a and 36a as the only isolable cycloadducts was examined by computational analysis. The geometry of the six-atom transition state was established by semiempirical methods by using the standard closed-shell, restricted Hartree-Fock (RHF) version of the AM1 method. With use of this constrained geometry for the six-membered pericyclic array, the overall conformational energies for the four possible transition states 52-55 were minimized by MM2 calculations (MacroModel). The calculated relative energies of these transition states were in the order 52 < 53 < 54 < 55. Since the cyclization of 34a produced only 35a and 36a in an approximately 9:1 ratio via the respective transition states 52 and 53, these calculations correlated qualitatively with the experimental results.
• BRANDS, KAREL M. J.;PANDIT, UPENDRA K., TETRAHEDRON LETT., 30,(1989) N1, C. 1423-1426
  作者：BRANDS, KAREL M. J.、PANDIT, UPENDRA K.

  DOI：——

  日期：——
• KRAUS, GEORGE A.;SHI, JIANMIN;REYNOLDS, DON, J. ORG. CHEM., 55,(1990) N, C. 1105-1106
  作者：KRAUS, GEORGE A.、SHI, JIANMIN、REYNOLDS, DON

  DOI：——

  日期：——