Name: metal-free synthesis of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts
Uploaded: 2015-02-24T14:00:00
Duration: 9 min 58 s
Description: Watch this Scientific Journal Video about Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts at JoVE.com

This work was supported by the UOIT start-up fund. We thank Mr. Matthew Baxter (UOIT) for his assistance in the laboratory.

1.合成Ynone的<ol><li>用分析天平，称量0.15毫摩尔所需钾alkynyltrifluoroborate盐（1.5当量），并加入到一个干净的小瓶中装有磁力搅拌棒。 </li><li>用装有针头的玻璃注射器柱塞，加入0.5毫升无水DCM中的小瓶，得到三氟的0.3M的溶液。 注：由于这是一个新的方法，反应已经进行了概念验证。为了减少浪费，他们已经在小范围内进行的。该反应可以按比例根据需要，以产生更大的产量。 </li><li>用玻璃注射器，加入0.15的1.0M的三氯化硼溶液毫摩尔（1.5当量，150微升）中的溶液，以在环境温度（20℃）搅拌下的反应容器中。更换帽。持或夹紧封端反应容器，使反应溶液低于水线的超声波仪。超声处理在20℃的溶液中30秒，频率ø˚F40千赫。 </li><li>在室温下搅拌（20℃）下另外20分钟反应溶液中。取决于alkynyltrifluoroborate起始材料的性质，观察颜色变化。从白色到黄褐色或黑褐色，红色或紫色颜色的变化是常见的。 </li><li>加入0.1毫摩尔的在所需的酰基氯（1.0当量），以在环境温度下的管形瓶（20℃）并搅拌。可替代地，将反应容器的内容物转移到装有磁力搅拌棒的烧瓶和0.1毫摩尔的酰氯。更换帽。在环境温度搅拌（20℃）下进行30分钟的反应液中。 注意：通常情况下，改变到非常暗的颜色是指示该反应的发生。 </li><li>使用薄层色谱（TLC）34监测反应通过用合适的酰氯标准进行比较的进展。 注意：根据所用原料的性质，反应可能不完全。在一个缸氯化物起始材料已被观察到了更高的运行点比对所有使用该方法制备迄今ynones的最终产品。 <ol><li>通过稀释大约10毫克的酰基氯为起始材料用1ml乙酸乙酯的小瓶制备的酰基氯的标准。 </li><li>用TLC点样器，当场在TLC板上的起跑线的反应溶液和标准。的共点与两个反应溶液和标准可能是有用的，以确定是否存在仍然起始原料存在于反应溶液中。 </li><li>通过试验和误差确定合适的薄层色谱的流动相。对于物品1a的制备，流动相组成为1:30的乙酸乙酯：己烷的结果在大约0.5和0.8的ynone产物和苯甲酰氯的 R F值分别原料。 </li><li>可视化在UV光下的开发TLC板上。用铅笔标注任何可见的斑点。 </li></ol></li></ol> 2.水后处理<ol><li>淬火通过添加1毫升的冷水（约5℃）到反应容器中的反应。使用巴斯德吸管，将溶液转移到一个干净的分液漏斗中。进一步稀释的分液漏斗中的内容，用10ml冷水和提取产物一旦在15ml乙酸乙酯中。 </li><li>弃去底部的水层，并用10毫升水和1的时间，用10ml盐水洗涤有机层1的额外时间。收集有机层到一个干净的锥形瓶中，并用硫酸镁干燥。过滤该溶液成利用重力过滤干净圆底烧瓶中。 </li></ol> 3.净化Ynone的<ol><li>采用薄层色谱法，确定一个合适的流动相对于所述产物的快速色谱法纯化。约0.5的保留因子（R f）为通常足以产物从任何剩余开始分离荷兰国际集团的材料和副产物。 注意：在分离度不佳的情况下，一个极性较小的溶剂系统可以用于使得该产品具有较低的Rf 值为 。因起始原料，一己烷的极性：1至5：在30〜乙酸乙酯混合物1一般是合适的。 </li><li>制备的含二氧化硅柱用合适的流动相湿。加了一层砂到塔的顶部，以便在加入产物和洗脱液，以避免扰乱二氧化硅。 </li><li>蒸发使用旋转蒸发器与浴温在40℃和旋转设定为120转的后处理溶液。溶解烧瓶的内容物在2 ml的流动相，并仔细均匀加载溶液上柱。确保该二氧化硅是湿但溶剂线不超过二氧化硅的高度。允许一些溶剂洗脱，使得产品的二氧化硅。添加少量的流动相重复。 </li><li>填写山坳UMN与在步骤3.1中确定的流动相;在物品1a的情况下，一个30：1的己烷：乙酸乙酯混合物是适当的。收集用快速色谱法以加速纯化过程在试管的级分。简单的适配器与管的空气出口连接。调节空气压力，使得洗脱液流过该柱以合适的速率。 </li><li>在TLC板上发现每一柱组分的。任选地，当场酰氯标准作为参考。用流动相认为适当步骤1.8开发TLC。马克在紫外光下可见的任何点，并指出，产品预计有较低的 R F比酰氯标准。 </li><li>收集含有可见的斑点成一个大圆底烧瓶中的所有分数。如果一个以上的点具有较低的 R F比起始材料存在，收集它们在单独的烧瓶中。用旋转蒸发器蒸除溶剂并干燥理解过程收集到的材料R为高电平真空两小时。 </li><li>如果需要的话，为了进一步纯化，从缺电子酰氯起始材料制备的ynone产品上执行一个小柱戊烷洗涤。在小规模，这可以使用巴氏吸管作为列执行。 <ol><li>溶解在最小量的氯仿中，DCM或二乙醚和负载的产品到硅胶柱上用戊烷湿。戊烷通过该柱洗脱1-2柱的长度，并收集到废烧杯中。 </li><li>洗脱使用乙醚或乙酸乙酯的戊烷塔的纯ynone产物。收集洗脱液在一个单独的烧瓶中，蒸发，并在高真空下放置了至少两小时。得到大约10毫克产物用于表征通过NMR光谱。 </li></ol></li></ol> Ynone 4.表征<ol><li>表征和评估使用1 H和13 C NMR谱的最终产品的纯度。34典型地，羰基碳的化学位移出现近177 ppm的在13 C NMR光谱。该ynone官能团的两个碳原子的SP由邻近87和93 ppm的特征峰来表示。 </li><li>用红外光谱仪34来识别ynone产物的特征羰峰。从相邻的三键电子离域通常会导致羰峰出现之间1600 1650 -1，这取决于该化合物的电子特性。 </li><li>确定产物的分子量，并使用高分辨率质谱进一步验证的身份。34 </li></ol>

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W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Expanded+substrate+scope+and+improved+reactivity+of+ether-forming+cross-coupling+reactions+of+organotrifluoroborates+and+acetals.">Expanded substrate scope and improved reactivity of ether-forming cross-coupling reactions of organotrifluoroborates and acetals.</a> J. Am. Chem. Soc. 133, 14082-14089 (2011).</li><li>Zeng, J., Vedachalam, S., Xiang, S., Liu, X. -. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+C-Glycosylation+of+Organotrifluoroborates+with+Glycosyl+Fluorides+and+Its+Application+to+the+Total+Synthesis+of+(+)-Varitriol.">Direct C-Glycosylation of Organotrifluoroborates with Glycosyl Fluorides and Its Application to the Total Synthesis of (+)-Varitriol.</a> Org. Lett. 13, 42-45 (2010).</li><li>Lehman, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+student's+lab+companion:+laboratory+techniques+for+organic+chemistry:+standard+scale+and+microscale.">The student's lab companion: laboratory techniques for organic chemistry: standard scale and microscale.</a> Pearson College Div. , (2008).</li><li>Molander, G. A., Cavalcanti, L. N., Canturk, B., Pan, P. -. S., Kennedy, L. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Hydrolysis+of+Organotrifluoroborates+via+Silica+Gel+and+Water.">Efficient Hydrolysis of Organotrifluoroborates via Silica Gel and Water.</a> 74, 7364-7369 (2009).</li><li>Molander, G. A., Ellis, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organotrifluoroborates:+protected+boronic+acids+that+expand+the+versatility+of+the+Suzuki+coupling+reaction.">Organotrifluoroborates: protected boronic acids that expand the versatility of the Suzuki coupling reaction.</a> Acc. Chem. Res. 40, 275-286 (2007).</li><li>Calloway, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel-Crafts+Syntheses.">The Friedel-Crafts Syntheses.</a> Chem. Rev. 17, 327-392 (1935).</li><li>Gore, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel-Crafts+acylation+reaction+and+its+application+to+polycyclic+aromatic+hydrocarbons.">The Friedel-Crafts acylation reaction and its application to polycyclic aromatic hydrocarbons.</a> Chem. Rev. 55, 229-281 (1955).</li><li>Groves, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel&#8211;Crafts+acylation+of+alkenes.">The Friedel&#8211;Crafts acylation of alkenes.</a> Chem. Soc. Rev. 1, 73-97 (1972).</li><li>Kim, B. J., Matteson, D. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conversion+of+alkyltrifluoroborates+into+alkyldichloroboranes+with+tetrachlorosilane+in+coordinating+solvents.">Conversion of alkyltrifluoroborates into alkyldichloroboranes with tetrachlorosilane in coordinating solvents.</a> Angew. Chem. 116, 3118-3120 (2004).</li><li>Thompson, L., Doraiswamy, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sonochemistry:+science+and+engineering.">Sonochemistry: science and engineering.</a> Ind. Eng. Chem. Res. 38, 1215-1249 (1999).</li></ol>

The authors declare that they have no competing financial interests.

表1示出了采取优化条件为苯乙炔三氟与苯甲酰氯反应，形成相应的ynone产物的步骤。最初，公知的organotrifluoroborates转换为organodifluoroboranes催化剂进行了测试。不幸的是硅胶，35四氯化硅，36和三氟化硼31,32没有促进形成所需ynone的（ 表1，条目1-3）。使用证明含氯路易斯酸催化剂，以获得更大的成功。在铁（III），氯化催化剂（ 表1，条目4）的存在下获得所需的ynone 1a的低收率。接着，铝（III），氯化了研究，作为其既定的能力，以促进在弗里德尔-克拉夫茨酰化oxocarbenium离子形成的结果。37-39需要的产物，产率62％时获得的铝（III），氯化催化剂为EMPloyed。 进一步的优化显示，空气和水分对反应的收率（ 表1，条目5-7）几乎没有影响。其结果是，随后的反应在非干燥的玻璃器皿中进行在空气的存在。尝试优化溶剂透露二氯甲烷（DCM）是特别适合的反应（ 表1，条目8-12）。在反应铝（III）氯化物催化的结果不一致促使替代性催化剂的探索。市售的铝（III），氯化六水合物是在反应条件（ 表1，条目13）下完全失活。这是一个很好的指标，铝（III），氯化水合物的形成抑制该反应。三氯化硼被发现产生类似的产量具有更好的一致性（ 表1，条目14）。 当钾alkynyltriflu互动oroborate用三氯化硼，更活泼的organodichloroborane物种形成。40该初始步骤是用于与酰氯的ynone并形成进行该反应的关键。因为organotrifluoroborate盐不溶于DCM中，将反应发生的非均相混合物。另外三氯化硼后，将溶液超声处理顺序通过增加三氟盐的可用以使该表面积，以促进形成反应二氯硼物种。超声波在反应混合物中的应用程序将导致通过空化气泡的产生机械影响。期间超声处理，空化气泡塌陷在流体导致高的温度和压力的局部区域41中冲击波产生的创建导致增加在固体三氟盐的动能微观湍流。期间超声促销系统中的能量的增加对三氟盐TES碎片而增加的表面积与三氯化硼交互。将反应混合物之前加入酰基氯为起始材料的超声处理保证了有效形成反应alkynyldichloroborane物种，而不需要更多的强制条件或更长的反应时间。 图2示出了当苯乙炔三氟用优化的反应条件下的各种酰氯的反应，所得到的结果。中性芳族（1B，1C）和脂族（1J-1）酰氯提供相应ynones在合成有用的产率。这些酰氯带有电子基团（1D-G）提供了良好的收益，而吸电子基团导致相对温和的收益率（1H，1I，1M）。有兴趣的朋友stingly，当吸电子基团位于邻位 （1I，59％），一显著产量增加相比于类似的对位观察取代的酰基氯（1H，30％）。该取代基中的邻位位置上的空间相互作用可能迫使羰基官能团出的平面，从而抵消了芳香环的吸电子性质。值得一提的是，4-溴丁酰氯反应，得到39％收率的所需产物1m上。据我们所知，这是第一个协议ynones合成容忍烷基溴官能团。偶尔，当酰基氯原料是中性或缺电子，脂族杂质出现在质子NMR。这可能需要一个戊烷洗涤以进一步提纯产物。虽然有可能，这是不经济的第一纯化S期期间执行戊烷洗因斯戊烷是昂贵相比己烷。二次纯化以较小规模分别完成诸如巴斯德吸管柱显著降低戊烷所需的量。 图3示出的alkynyltrifluoroborate盐的身份对反应产率的影响。在通常情况下，芳环上的苯基乙炔三氟盐轴承的给电子取代基的衍生物反应，用芳族和脂族酰基的氯化物，以产生所需的ynones良好至优良产率（2A-2C，3A-C）。脂族alkynyltrifluoroborate盐证明是较低反应性的底物。当hexynyl-和cyclopentylethynyltrifluoroborate盐进行反应与富电子苯甲酰氯衍生物（4α，5α）适度的产量已经被获得。 总之，新方法的编写Øf起酰基氯化物和钾alkynyltrifluoroborate盐ynones已经研制成功。通过该方法的范围从温和到优良取决于酰氯的性质获得ynones的合成收率和三氟起始原料。在一般的那些起始物承载给电子取代基进行反应更容易地比起始材料轴承中性和吸电子官能团。这种方法的价值在于方法的操作简便性和官能团的耐受性。这种直接的，一锅反应在环境温度下在三氯化硼的存在下迅速进行，而不排斥空气和湿气的。这种简便的方法可以采用ynones的制剂谦虚良好的收益从各种酰氯和alkynyltrifluoroborate盐。

The intention of this video is to demonstrate a straightforward approach for the preparation of compounds containing an ynone functional group from convenient starting materials. Ynones are valuable building blocks in organic chemistry that have been shown to have biomedical and material significance. Ynones are precursors to valuable organic functional groups including pyrimidines,1,2 quinolones,3 furans,4 pyrazoles,5,6 flavones,7 oximes,8 and chiral propargylic alcohols.9-11 A more convenient method for the preparation of ynones has been sought as a result of the drawbacks of traditional methods including poor functional group tolerance and tedious synthetic routes.
The reaction of metal12,13 and metalloid14 acetylides with acyl chlorides is one common route for the preparation of ynones. Alternatively, the synthesis of ynones from acyl chloride can be achieved via two-step procedures using Weinreb amides and organolithium or Grignard reagents.15 Another prevalent approach includes the addition of organolithium or Grignard reagents to an aldehyde, which is followed by the oxidation of a secondary alcohol to the corresponding ketone.16-19 Poor functional group tolerance of metal acetylides and the need to purify synthetic intermediates after each step are main deficiencies of the aforementioned methods. Transition-metal-catalyzed carbonylative couplings have recently emerged as an alternative approach for the preparation of ynones.20-22 Unfortunately, in addition to cost and toxicity associated with transition metals, metal-catalyzed carbonylative reactions often require elevated CO pressures and suffer from the presence of an undesired Sonogashira coupling byproduct. Given their utility in organic synthesis as well as the drawbacks associated with traditional synthetic methods, the development of a more straightforward method for the preparation of ynones is appealing.
Potassium organotrifluoroborate salts have recently emerged as versatile reagents in organic synthesis. Advantages including ease of preparation,23 inherent stability, low toxicity, and good functional group tolerance have made organotrifluoroborate salts attractive synthetic reagents.24-27 Organotrifluoroborate salts have been used primarily as a bench-stable equivalent of boronic acids for palladium-catalyzed Suzuki-Miyaura coupling.26 Recently, following a seminal work by Matteson and co-workers,28 Bode, Molander and others have highlighted the utility of organotrifluoroborates as reagents in non-metal catalyzed reactions.29-33 The field of transition-metal-free reactions of trifluoroborates is still in its infancy stage. Given the great potential for use of organotrifluoroborate salts in non-metal catalyzed organic synthesis, we sought to develop a novel method for the preparation of ynones from acyl chlorides and alkynyltrifluoroborate salts.

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Name of Material/ Equipment</td>
			<td style="width:71px;">Company</td>
			<td style="width:119px;">Catalog Number</td>
			<td style="width:167px;">Comments/Description</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sonicator</td>
			<td style="width:71px;">VGT</td>
			<td style="width:119px;">1860QT</td>
			<td>Ultrasonic cleaner. Similar sonication devices may be used.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Dichloromethane</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">270997</td>
			<td>Anhydrous</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Boron trichloride solution&#160;</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">178934</td>
			<td>1M solution in DCM</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Acyl chloride</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">Various</td>
			<td>Acyl chlorides from other suppliers such as Alfa Aesar may be used. Caution - refer to MSDS for safety information.</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Potassium alkynyltrifluoroborate salt</td>
			<td style="width:71px;">N/A</td>
			<td style="width:119px;">N/A</td>
			<td>Synthesized23 from terminal alkyne</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ethyl acetate</td>
			<td style="width:71px;">ACP</td>
			<td style="width:119px;">E-2000</td>
			<td>ACS grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Hexanes</td>
			<td style="width:71px;">ACP</td>
			<td style="width:119px;">H-3500</td>
			<td>ACS grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Pentane</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">236705</td>
			<td>Anhydrous</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Magnesium sulfate</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">M7506</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Filter paper</td>
			<td style="width:71px;">Whatman</td>
			<td style="width:119px;">1093 126</td>
			<td>Student grade. This speceific variety is not necessary.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Silica Gel 60</td>
			<td style="width:71px;">EMD</td>
			<td style="width:119px;">1.11567.9026</td>
			<td>Particle size 0.040-0.063</td>
		</tr>
	</tbody>
</table>

metal-free synthesis of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride.

最初的努力都集中围绕由苯乙炔三氟S1和苯甲酰氯（ 图1）的制备ynone 1a的。 表1示出了优化步骤来执行，包括各种路易斯酸，溶剂，以及检查的水对反应的影响的筛选。接着，将反应的范围已探索通过提交苯乙炔三氟到优化条件下在各种酰氯的存在（ 图2）。温和至优异的产量可取决于酰氯衬底的性质而获得。该反应的范围已进一步通过alkynyltrifluoroborate盐的几个其他示例的准备进行评价。 图3示出了可以在开发的条件下ynones的制备可以采用其他alkynyltrifluoroborate盐中的例子。啉衍生物ylacetylene三氟轴承电子捐赠取代给予相应的ynone产品优良率，而alkynyltrifluoroborate盐的脂肪族衍生物被证明是略少反应，得到适度的产量。 <img alt="图1" src="/files/ftp_upload/52401/52401fig1highres.jpg" /> 图1：示出了用于ynone 1a的制备包括形成反应性中间体二氯硼烷的条件从苯乙炔三氟S1和苯甲酰氯方案制备Ynone 1a的 。 <img alt="图2" src="/files/ftp_upload/52401/52401fig2highres.jpg" /> 图2：ynone 1a的代表1 H NMR谱的化学位移和特性的质子的相对积分来标记。 图3：ynone 1a的代表。13 C NMR光谱特性的碳的化学位移被标记。 <img alt="图4" src="/files/ftp_upload/52401/52401fig4highres.jpg" /> 图4： 通过常压化学电离得到ynone 1a的代表性的HRMS光谱的[M + H]所述的测定m / z值+离子被报告。 <img alt="图5" src="/files/ftp_upload/52401/52401fig5highres.jpg" /> 图5：phenylacetylenetrifluoroborate盐S1反应与酰基氯的结构和产率通过改变身份生产的产品。酰基氯的原料的图示。反应运行与1当量的酰氯，1.5当量钾phenylacetylenetrifluoroborate S1中，与1.5当量的三氯化硼。 <img alt="图6" src="/files/ftp_upload/52401/52401fig6highres.jpg" /> 图6：不同alkynyltrifluoroborates与酰氯的结构和产率通过改变alkynyltrifluoroborate原料的身份生产的产品的反应如下所示。反应运行与1当量的酰氯，2.5当量钾organotrifluoroborate盐和2.5当量的三氯化硼。 <table border="0" cellpadding="0" cellspacing="0"><tbody><tr><td> 输入 </td><td> 路易斯酸 </td><td> 路易斯酸（当量） </td><td> 条件 </td><td> 产量（％） </td></tr><tr><td> 1 B &lt;/ SUP&gt; </td><td> SiO 2的</td><td> 16.5 </td><td> 的 CH 2 Cl 2 </td><td> 0 </td></tr><tr><td> 2 </td><td> 四氯化硅</td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td>跟踪</td></tr><tr><td> 3 </td><td> BF 3·OET 2 </td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td>跟踪</td></tr><tr><td> 4 B </td><td> 氯化铁</td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 24 </td></tr><tr><td> 5℃ </td><td> 3氯化铝</td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 62 </td></tr><tr><td> 6天</td><td> 3氯化铝</td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 66 </td></tr><tr><td> 7ê </td><td> 3氯化铝</td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 60 </td></tr><tr><td> 8 </td><td> 3氯化铝</子&gt; </td><td> 1 </td><td> THF </td><td>跟踪</td></tr><tr><td> 9 </td><td> 3氯化铝</td><td> 1 </td><td>甲苯</td><td>跟踪</td></tr><tr><td> 10 </td><td> 3氯化铝</td><td> 2 </td><td> CLCH 2的CH 2 Cl </td><td> 33 </td></tr><tr><td> 11 </td><td> 3氯化铝</td><td> 1 </td><td> DMSO </td><td>跟踪</td></tr><tr><td> 12 </td><td> 3氯化铝</td><td> 2 </td><td>乙腈</td><td>跟踪</td></tr><tr><td> 13 </td><td>氯化铝3·6H 2 O </td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 0 </td></tr><tr><td> 14 B </td><td> BCL 3 </td><td> 1.5 </td><td> 的 CH 2 Cl 2 </td><td> 67 </td></tr><tr><td> 15 </td><td> BBR 3 </td><td> 1 </td><td> 的 CH 2 Cl 2 </td><td> 20 </td></tr></tbody></table><stro纳克&gt;表1：产品的优化条件，供的ynone 1a 上的制备产率 1a的反应条件和路易斯酸催化剂的变化时。 一个反应是运行用1当量苯甲酰氯和1当量的钾phenylacetylenetrifluoroborate S1。B 1.5当量S1。Ç无水条件D中的反应物在空气下的非干燥的玻璃器皿进行即无水条件+1微升水中。

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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

Ynones从酰氯和钾Alkynyltrifluoroborate盐无金属合成

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups ...

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