1-(trimethylsilyl)-2-methyl-2-butene | 18293-98-6

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: 1-(trimethylsilyl)-2-methyl-2-butene
• 英文别名: 1-Trimethylsilyl-2-methyl-but-2-en；2-Methyl-1-trimethylsilyl-but-2-en；trimethyl-(2-methyl-but-2-enyl)-silane；Trimethyl-(2-methyl-but-2-enyl)-silan；2-Methyl-2-butenyltrimethylsilane；trimethyl(2-methylbut-2-enyl)silane
• CAS: 18293-98-6
• 化学式: C₈H₁₈Si
• 分子量: 142.316
• InChiKey: RAWXBPMMKFPULX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-(trimethylsilyl)-2-methyl-2-butene 在 (2R,3R)-2-O-(2,6-diisopropoxybenzoyl)tartaric acid 、 四丁基氟化铵 、 3,5-双(三氟甲基)苯硼酸 作用下， 以 四氢呋喃 为溶剂， 生成 (E)-4-Hydroxy-2,3-dimethyl-6-phenyl-1,5-hexadiene
  参考文献：
  名称：

  Catalytic asymmetric allylation using a chiral (acyloxy)borane complex as a versatile Lewis acid catalyst

  摘要：

  In the presence of 20 mol % of a chiral (acyloxy)borane (CAB) complex prepared from (2R,3R)-2-O-(2,6-diisopropoxybenzoyl)tartaric acid and borane-tetrahydrofuran, various allyltrimethylsilanes react with achiral aldehydes to afford the corresponding homoallylic alcohols in good yields with high diastereo- and enantioselectivities. Furthermore, the reactivity of allylation can be improved without reducing the enantioselelctivity by using 10-20 mol % of the CAB complex prepared from 3,5-bis(trifluoromethyl)phenylboronic acid and chiral tartaric acid derivative. The observed selectivities and re-face attack of nucleophiles on the carbonyl carbons of aldehydes imply that the extended transition-state model is applicable.

  DOI：

  10.1021/ja00077a054
• 作为产物：
  描述：

  2-methyl-3-(trimethylsilylmethyl)but-3-enoic acid 130.0~150.0 ℃ 、101.32 kPa 条件下， 反应 1.0h， 以92%的产率得到1-(trimethylsilyl)-2-methyl-2-butene
  参考文献：
  名称：

  3-三甲基甲硅烷基甲基二烯酸酯的区域和立体选择性烷基化。3-烷基化的2-甲基烯丙基硅烷的新型合成

  摘要：

  从容易获得的3-三甲基甲硅烷基甲基-3-丁烯酸及其甲酯得到的3-三甲基甲硅烷基甲基二烯酸锂和铜阴离子进行区域选择性和立体选择性烷基化。通过热解，α-烷基化产物易于转化为3-烷基化2-甲基烯丙基硅烷。

  DOI：

  10.1016/s0040-4039(01)90413-7

文献信息

• Ru-Catalyzed Alkene−Alkyne Coupling. Total Synthesis of Amphidinolide P
  作者：Barry M. Trost、Julien P. N. Papillon、Thomas Nussbaumer

  DOI：10.1021/ja055967n

  日期：2005.12.1

  unsaturated ruthenium complex catalyzed the formation of a carbon-carbon bond between two judiciously chosen alkene and alkyne partners in good yield, and in a chemo- and regioselective fashion, despite the significant degree of unsaturation of the substrates. The resulting 1,4-diene forms the backbone of the cytotoxic marine natural product amphidinolide P. The alkene partner was rapidly assembled from (R)-glycidyl

  尽管底物具有显着的不饱和度，但配位不饱和钌络合物以良好的产率、化学和区域选择性的方式催化了两个精心选择的烯烃和炔烃伙伴之间碳-碳键的形成。由此产生的 1,4-二烯形成了细胞毒性海洋天然产物两栖内酯 P 的骨架。烯烃伴侣由 (R)-甲苯磺酸缩水甘油酯快速组装而成，它是单瓶连续三组分偶联过程的关键使用乙烯基锂和乙烯基氰铜酸酯。炔烃配偶体的合成利用了在螯合控制条件下由顺式乙酸衍生的烯丙基锡试剂的不寻常的反选择性加成。此外，还具有使用偶氮二羧酸酯-三苯基膦系统的显着E选择性E2工艺。还介绍了使用 β-内酯作为热力学弹簧来实现大内酯化的第一个例子。因此，氧杂环丁酮环被用作有效的保护基团，提高了该全合成的整体效率。这项工作也是进一步探讨钌催化的烯烃-炔烃偶联范围的机会，特别是使用烯炔，并描述了使用各种官能化底物的研究。
• Triflimide-catalyzed allylsilane annulations of benzylic alcohols for the divergent synthesis of indanes and tetralins
  作者：Jordan C. T. Reddel、Weiwei Wang、Kalli Koukounas、Regan J. Thomson

  DOI：10.1039/c6sc04762a

  日期：——

  development of a triflimide-catalyzed annulation of benzylic alcohols with allylsilanes for the synthesis of indane or tetralin structures is reported. In this fragment coupling reaction, complexity is built rapidly from readily available starting materials to yield diverse sets of products with up to three contiguous stereocenters. Indanes or tetralins can be generated from common precursors depending

  据报道，用三氟甲酰亚胺催化的苄醇与烯丙基硅烷的环合反应可用于茚满或四氢化萘结构的合成。在这种片段偶联反应中，从容易获得的起始原料迅速建立了复杂性，以产生具有多达三个连续立体中心的多种产品。取决于所使用的烯丙基硅烷试剂的结构，茚满或四氢化萘可以从常见的前体中生成。几种木脂素天然产物的简洁合成突显了这种新设计方法的实用性。
• Kucharskaja et al., Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1958, p. 1372,1374;engl.Ausg.S.1323,1325
  作者：Kucharskaja et al.

  DOI：——

  日期：——
• Alkene−Alkyne Coupling as a Linchpin:  An Efficient and Convergent Synthesis of Amphidinolide P
  作者：Barry M. Trost、Julien P. N. Papillon

  DOI：10.1021/ja045449x

  日期：2004.10.1

  A short and efficient synthesis of the cytotoxic macrolide amphidinolide P is described. A remarkably chemo- and regioselective ruthenium-catalyzed alkene-alkyne coupling allows for a convergent synthesis and demonstrates that both enynes and beta-lactones are suitable coupling partners. This work also features a novel strategy for the preparation of macrolactones via intramolecular transesterification of beta-lactones. The target structure was prepared in 15 steps for the longest linear sequence and 10% overall yield, 24 steps total.
• Catalytic asymmetric allylation using a chiral (acyloxy)borane complex as a versatile Lewis acid catalyst
  作者：Kazuaki Ishihara、Makoto Mouri、Qingzhi Gao、Tohru Maruyama、Kyoji Furuta、Hisashi Yamamoto

  DOI：10.1021/ja00077a054

  日期：1993.12

  In the presence of 20 mol % of a chiral (acyloxy)borane (CAB) complex prepared from (2R,3R)-2-O-(2,6-diisopropoxybenzoyl)tartaric acid and borane-tetrahydrofuran, various allyltrimethylsilanes react with achiral aldehydes to afford the corresponding homoallylic alcohols in good yields with high diastereo- and enantioselectivities. Furthermore, the reactivity of allylation can be improved without reducing the enantioselelctivity by using 10-20 mol % of the CAB complex prepared from 3,5-bis(trifluoromethyl)phenylboronic acid and chiral tartaric acid derivative. The observed selectivities and re-face attack of nucleophiles on the carbonyl carbons of aldehydes imply that the extended transition-state model is applicable.