1-iodo-3-t-butyldimethylsilyloxyl-1-propyne | 159009-86-6

• 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-iodo-3-t-butyldimethylsilyloxyl-1-propyne
• 英文别名: 3-iodo-2-propyn-1-ol；1-Iodo-3-(tert-butyldimethylsiloxy)-1-propyne；tert-butyl-(3-iodoprop-2-ynoxy)-dimethylsilane
• CAS: 159009-86-6
• 化学式: C₉H₁₇IOSi
• 分子量: 296.223
• InChiKey: BIXHKILJWKFKOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-iodo-3-t-butyldimethylsilyloxyl-1-propyne 在 甲醇 、 四(三苯基膦)钯 、 正丁基锂 、 bis(cyclohexanyl)borane 、 potassium carbonate 、 magnesium 、 溶剂黄146 、 zinc(II) chloride 作用下， 反应 8.75h， 生成 methyl cis-9-(tert-butyldimethylsiloxy)-7-nonen-2-ynoate
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015
• 作为产物：
  描述：

  叔丁基二甲基(2-丙炔氧基)硅烷 在 正丁基锂 、 碘 作用下， 以 四氢呋喃 为溶剂， 以50%的产率得到1-iodo-3-t-butyldimethylsilyloxyl-1-propyne
  参考文献：
  名称：

  对映异构纯顺式-环丙基硼酸酯的合成

  摘要：

  高度稳定的对映体纯环丙基硼酸酯是制备大量不同环丙烷衍生物的理想结构单元。虽然反式构型化合物被证明是容易获得的，但我们在此报告了相应顺式环丙烷的首次合成。将讨论此过程的范围和限制。产品的绝对构型可以通过化学和光谱相关来确定。

  DOI：

  10.1002/1099-0690(200007)2000:14<2557::aid-ejoc2557>3.0.co;2-i

文献信息

• Synthesis of the Proposed Structure of Mucoxin via Regio- and Stereoselective Tetrahydrofuran Ring-Forming Strategies
  作者：Radha S. Narayan、Babak Borhan

  DOI：10.1021/jo052073c

  日期：2006.2.1

  1.0 × 10-2 μg/mL). The total synthesis described herein features two regio- and stereoselective THF ring-forming reactions. The 2,3,5-trisubstituted THF portion (C13−C17) was accessed using a highly regioselective cyclization of a methylene-interrupted epoxydiol, and the 2,5-disubstituted THF ring (C8−C12) was conveniently assembled via a 1,2-n-triol cyclization strategy. The spectral data of the synthetic

  描述了提议的粘蛋白（1）结构的对映选择性全合成。粘液毒素是一种从卷花粘膜的生物活性叶片提取物中分离出来的无水产乙酸素，它是第一种含有羟基化三取代四氢呋喃（THF）环的产乙酸素。此天然产物是一种高度有效的和特异性的抗肿瘤抗MCF-7（乳腺癌）细胞系剂（ED 50 = 3.7×10 - 3微克/毫升相比阿霉素，ED 50 = 1.0×10 - 2微克/毫升）。本文所述的总合成具有两个区域选择性和立体选择性的THF成环反应。2,3,5-三取代的THF部分（C13-C17）使用亚甲基间断的环氧二醇的高度区域选择性环化获得，2,5,5-二取代的THF环（C8-C12）可以通过1方便地组装2-正三醇环化策略。合成材料及其两个非对映异构体的光谱数据与天然产物的报道数据不匹配。在对合成分子进行详细的光谱分析的基础上，我们认为光谱差异是由于天然产物的立体化学错配引起的。
• Asymmetric synthesis of Pachastrissamine (Jaspine B) and its diastereomers viaη3-allylpalladium intermediates
  作者：Mikko Passiniemi、Ari M. P. Koskinen

  DOI：10.1039/c0ob00643b

  日期：——

  A short route for the synthesis of Pachastrissamine (Jaspine B), an anhydrosphingosine derivative, and all three of its diastereomers is presented. The route consists of only 9 steps from the commercially available Garner's aldehyde. The furan framework is formed via an η3-allylpalladium intermediate.

  合成以下物质的捷径 Pachastrissamine （茉莉花B），脱水鞘氨醇衍生物及其所有三个非对映异构体。该路线仅由市售Garner醛中的9个步骤组成。呋喃框架形成经由一个η 3 π-烯丙基中间体。
• An Atom-Economic and Selective Ruthenium-Catalyzed Redox Isomerization of Propargylic Alcohols. An Efficient Strategy for the Synthesis of Leukotrienes
  作者：Barry M. Trost、Robert C. Livingston

  DOI：10.1021/ja804105m

  日期：2008.9.10

  secondary propargylic alcohols in good yields to provide trans enals and enones exclusively. Readily available indenylbis(triphenylphosphine)ruthenium chloride, in the presence of indium triflate and camphorsulfonic acid, gives the best turnover numbers and reactivity with the broadest range of substrates. Deuterium labeling experiments suggest that the process occurs through propargylic hydride migration

  催化钌配合物与铟助催化剂和布朗斯台德酸一起以良好的产率异构化伯醇和仲炔醇，以专门提供反式烯醛和烯酮。在三氟甲磺酸铟和樟脑磺酸存在下，现成的茚基双（三苯基膦）氯化钌可提供最佳的转化率和对最广泛底物的反应性。氘标记实验表明，该过程是通过炔丙基氢化物迁移随后产生的乙烯基钌中间体的质子裂解发生的。这种方法在白三烯 B4 的合成中的应用证明了它的实用性和非凡的选择性。
• Copper mediated scalemic organolithium reagents in alkaloid syntheses
  作者：R. Karl Dieter、Ningyi Chen、Rhett T. Watson

  DOI：10.1016/j.tet.2005.01.094

  日期：2005.3

  with THF soluble CuCN·2LiCl react with ω-functionalized vinyl halides to afford 2-alkenyl-N-Boc-pyrrolidines. N-Boc deprotection and cyclization via intramolecular N-alkylation generates the pyrrolizidine or indolizidine skeletons. Subsequent functional group manipulation affords enantioenriched (+)-heliotridane, (+)-isoretronecanol, a formal synthesis of (+)-laburnine, (+)-(R)-2,3,5,7a-tetrahydro-1H-pyrrolizine

  通过N - Boc-吡咯烷的不对称去质子化，然后用可溶于THF的CuCN·2LiCl处理，生成ω-官能化的乙烯基卤化物，生成2-甲基吡咯烷基铜酸酯，得到2-烯基-N - Boc-吡咯烷。N- Boc脱保护和通过分子内N-烷基化的环化反应生成吡咯并立定或吲哚并立定骨架。随后的官能团操作提供了对映体富集的（+）-三碘三环乙烷，（+）-异戊烯醇，（+）-金丝氨酸，（+）-（R）-2,3,5,7a-四氢-1 H-吡咯嗪的正式合成物，（R）-1,2,3,5,6,8a-六氢吲哚嗪，（+）- ent -δ-可耐碱，（+）-tashiromine和（+）-5-epitashiromine。
• One-step recyclization of sugar acetylenes to form medium ether rings via dicobalthexacarbonyl complexes
  作者：Chavi Yenjai、Minoru Isobe

  DOI：10.1016/s0040-4020(98)00013-1

  日期：1998.3

  were recyclized upon treatment with acid to form the medium size (7, 8, 9 and 10 membered) ether rings. The crucial mechanism was cis-trans double bond isomerization of allylic cation connected to dicobalthexacarbonyl complexes. Decomplexation was successfully achieved under high pressure hydrogenation by using rhodium catalyst.

  将四个C-1炔基化D-葡萄糖转化为相应的二钴六羰基配合物。在用酸处理后将它们全部再循环以形成中等大小的（7、8、9和10元）醚环。关键机制是与二钴六羰基配合物连接的烯丙基阳离子的顺反双键异构化。通过使用铑催化剂，在高压加氢下成功实现了分解。