这项工作由汉密尔顿学院和爱德华和弗吉尼亚泰勒基金资助, 用于学生/教员的化学研究。

1. 合成n-磺唑 2a: (2-(1-磺-1H-12, 3-唑-4-基) 苯基) 甲醇
<ol>
	<li>添加一个 3 x 10 mm 聚四氟乙烯磁性搅拌棒, 139 毫克 2 ethynylbenzyl 酒精, 和20毫克的铜 (I) 吩 (CuTC) 的烤箱干 2-5 毫升微波瓶和密封瓶安全与隔膜帽和机。由于微波的快速加热, 总是使用新的小瓶和无任何缺陷的瓶盖, 并确保瓶盖是安全和适当的安装。</li>
	<li>真空下从瓶子中取出空气, 再用氩气充三次。</li>
	<li>通过注射器加入4毫升无水氯仿, 开始磁搅拌。</li>
	<li>添加0.15 毫升的 p-磺叠氮化物 (tsn-3) 滴通过注射器。警告!p-磺叠氮化物可能是爆炸性的28 , 必须使用适当的个人防护设备进行处理。</li>
	<li>将密封的微波瓶在100° c 的微波反应器中加热15分钟.警告!请勿使用标准微波炉或未经授权的化学合成设备。 注: 本协议采用商用微波反应器。吸收水平设置为 "正常", 搅拌速度保持在每分钟600轮换 (RPM)。其他的用于化学合成的微波反应器也可能适用于该协议, 尽管理想的时间、温度和其他参数可能会有所不同。</li>
	<li>用压缩空气流将反应釜冷却到室温 (〜 2-3 分钟), 然后将反应混合物转移到100毫升的圆底烧瓶。用额外的 2 x 10 毫升的二氯甲烷清洗反应瓶, 将任何残留的原油转移到100毫升圆底烧瓶中。</li>
	<li>加入〜1.5 克硅胶到相同的圆形底瓶和去除溶剂使用旋转蒸发器。</li>
	<li>紧密包装硅胶吸附与粗产品成一个固体负载墨盒和附加到一个12克包装硅胶柱自动闪光色谱。 注: 本协议采用了自动净化系统、固体负载墨盒和12克硅胶柱。溶剂流动率维持在大约30毫升/分钟. 自动闪光色谱法是不需要纯化的;传统的闪光层析也可以使用。但是, 我们支持自动化, 因为它通常使人能够在发生重大分解之前尽快隔离复合2a 。</li>
	<li>运行该列使用连续梯度 0-100% 乙酸乙酯在 hexanes 超过15分钟, 开始与纯 hexanes 和结束纯乙酸乙酯。收集的主要峰值, 由紫外线吸收在 254 nm 和集中的组合, 相应的分数在一个旋转蒸发器获得纯化产品2a作为一个白色固体。 注: 三唑2a通常在氩气下以 2-5 ° c 储存 1-2 周时被发现是稳定的。但是, 某些批次的产品降解速度较快, 可能是由于来自 CDCl3的 DCl 污染。因此, 我们建议通过使用 CDCl3中和与 K2CO3并立即在随后的反应中使用它来分析产品的纯度, 从而取得最佳效果。</li>
</ol>
2. 合成N-(2-alkoxyvinyl) 磺酰胺 phthalan 3a: (Z)-N-(呋喃-1 (3H)-ylidenemethyl)-4-methylbenzenesulfonamide
<ol>
	<li>添加一个 3 x 10 mm 聚四氟乙烯磁性搅拌棒和4.6 毫克的铑 (II) 乙酸二聚体的烤箱干 0.5-2 毫升微波瓶和密封瓶安全的隔膜帽和机。由于微波的快速加热, 总是使用新的小瓶和无任何缺陷的瓶盖, 并确保瓶盖是安全和适当的安装。</li>
	<li>真空下从瓶子中取出空气, 再用氩气充三次。</li>
	<li>在氩气气氛下, 在1毫升的无水氯仿中溶解152毫克的三唑2a , 然后通过注射器将得到的溶液转移到微波容器。用额外的2毫升氯仿将含有残余三唑的烧瓶冲洗两次, 并将其转移到同一微波容器中, 以确保所有起始物料都被转移。</li>
	<li>将密封的微波瓶在100° c 的微波反应器中加热 1 h.警告!请勿使用标准微波炉或未经授权的化学合成设备。 注: 本协议采用商用微波反应器。吸收水平设置为 "正常", 搅拌速度保持在每分钟600轮换 (RPM)。其他的用于化学合成的微波反应器也可能适用于该协议, 尽管理想的时间、温度和其他参数可能会有所不同。</li>
	<li>用一股压缩空气和过滤器通过短的硅胶, 用乙酸乙酯洗脱, 将反应容器冷却到室温下 (〜 2-3 分钟)。</li>
	<li>将滤液在真空中, 使用带有温暖 (〜30° c) 水浴的旋转式蒸发器, 以获得足够纯度的产品, 以便立即用于随后的反应。 
	注意产品快速分解 (在1h 以内), 如在 CDCl3中含有残余 DCl 的轻度酸性条件下, 并逐渐 (在 1-3d 以内), 当在氩下在 3-5 ° c 下储存整齐时。因此, 我们建议通过使用 CDCl3中和与 K2CO3并立即在随后的反应中使用它来分析产品的纯度, 从而取得最佳效果。</li>
	<li>如有必要, 通过用 0-75% 梯度的乙酸乙酯在 hexanes 超过15分钟, 从纯 hexanes 开始, 以75% 乙酸乙酯在 hexanes。 注: 本协议采用了自动净化系统、固体负载墨盒和12克硅胶柱。溶剂流动率维持在大约30毫升/分钟. 自动闪光色谱法是不需要纯化的;传统的闪光层析也可以使用。但是, 我们支持自动化, 因为它通常使人能够在发生重大分解之前尽快隔离复合3a 。</li>
</ol>
3。Phthalan 4 的合成: N-((13-dihydroisobenzofuran-1-基) 甲基)-4-methylbenzenesulfonamide
<ol>
	<li>在一个25毫升的圆形底瓶与磁性搅拌棒, 溶解211毫克新鲜制备的 phthalan 3a在15毫升的绝对乙醇在氩气气氛下。</li>
	<li>在碳瓶上加入149毫克的 10% 钯, 注意尽量减少暴露在空气中。警告!确保反应混合物在氩气或氮气气氛下是非常重要的。碳钯可以在空气、氢气和/或易燃溶剂的存在下点燃。佩带所有适当的个人防护设备, 并主动在附近放置一个灭火器和/或一桶沙子来扑灭火焰。</li>
	<li>用氢气把标准的乳胶气球装在注射器上。请勿超过建议的气球容量。</li>
	<li>用针头将气球和注射器连接到反应血管, 穿透隔膜。检查以确保气球和/或隔膜没有泄漏。</li>
	<li>用氢气代替氩气, 在将球囊捏出时, 在反应釜上应用微弱的真空, 然后在停止真空后, 用氢气填充容器。重复两次。</li>
	<li>搅拌24小时的反应, 然后取出气球。</li>
	<li>用氩气清洗烧瓶, 然后通过硅胶塞洗液和乙酸乙酯过滤溶液。小心丢弃含有钯的硅胶, 并将其与水混合, 放入密封的固体废物容器内。</li>
	<li>将溶剂在真空中删除以提供产品。</li>
</ol>
4. 乙胺5的合成: N-(2-(羟甲基) 苯乙基)-4-methylbenzenesulfonamide
<ol>
	<li>在一个10毫升的圆形底瓶, 溶解169毫克新鲜制备的 phthalan 3a与5毫升乙醚下的氩气气氛。</li>
	<li>冷却反应混合物到0° c 使用冰浴, 然后慢慢地增加0.52 毫升的 60% 溶液的钠双 (2-氧) 铝氢化物在甲苯。警告!二 (2-氧) 氢化钠与水发生剧烈反应。仅在无湿气、惰性的气氛中使用此试剂。</li>
	<li>室温下将反应混合物搅拌18小时。</li>
	<li>冷却反应混合物到0° c, 然后小心地加入0.5 毫升的甲醇滴超过2分钟搅拌为一个额外的2分钟, 在0° c。警告!将甲醇添加到双 (2-氧) 铝氢化物是放热的。确保解决方案足够冷, 并注意避免同时添加甲醇。</li>
	<li>在0° c 时, 加入0.6 毫升饱和水氯化铵, 除去冰浴, 在室温下搅拌5分钟。</li>
	<li>将所得到的溶液倒入含有90毫升1M 盐酸的分漏斗中, 并提取60毫升乙酸乙酯三倍的水层。</li>
	<li>用30毫升水和30毫升盐水洗涤混合的有机层, 然后在硫酸钠上烘干。</li>
	<li>使用傅书礼漏斗过滤硫酸钠, 并将滤液集中在真空中, 以获得粗乙胺产品。 注意: 通常, 该产品在这一步之后是足够纯的, 但偶尔会出现来自N的分解 (2-alkoxyvinyl) 磺胺 phthalan 3a的污染物。</li>
	<li>如有必要, 用 0-100% 梯度的乙酸乙酯在 hexanes 超过15分钟, 从纯 hexanes 开始, 以纯乙酸乙酯结束, 通过柱层析在硅胶上提纯产品。 注: 本协议采用了净化系统、固体负载盒和12克硅胶柱。溶剂流动率维持在大约30毫升/分钟. 自动闪光色谱法是不需要纯化的;传统的闪光层析也可以使用。</li>
</ol>
5. 酮6c 的合成: N-((1-(2-基)-13-dihydroisobenzofuran-1-基) 甲基)-4-methylbenzenesulfonamide
<ol>
	<li>在一个10毫升的圆底烧瓶与搅拌棒, 溶解211毫克新鲜合成 phthalan 3a在2毫升的乙二醇下空气气氛和开始搅拌。</li>
	<li>使用1毫升注射器配备18针, 增加1滴三甲基硅氯的搅拌解决方案。</li>
	<li>将橡胶隔膜放在烧瓶上, 用透气针将空气打开, 并在室温下搅拌18小时的反应混合物。</li>
	<li>将反应混合物转移到125毫升分漏斗, 用50毫升的二氯甲烷冲洗, 然后加入10毫升饱和水碳酸氢钠和40毫升去离子水。</li>
	<li>用力搅拌, 经常排气, 并将有机层分离成干净的烧瓶。每次用30毫升的二氯甲烷萃取额外的三次水层。</li>
	<li>结合有机层和干硫酸钠。</li>
	<li>用傅书礼漏斗过滤硫酸钠, 将滤液集中在旋转蒸发器上。</li>
	<li>在10毫升的二氯甲烷中溶解原油, 在混合物中加入 ~ 750 毫克的硅胶, 用旋转蒸发器除去溶剂。</li>
	<li>紧密包装硅胶吸附与粗产品成一个固体负载墨盒和附加到一个12克包装硅胶柱自动闪光色谱。 注: 本协议采用了净化系统、固体负载盒和12克硅胶柱。溶剂流动率维持在大约30毫升/分钟. 自动闪光色谱法是不需要纯化的;传统的闪光层析也可以使用。</li>
	<li>运行该列使用连续梯度 0-70% 乙酸乙酯在 hexanes 超过15分钟, 开始与纯 hexanes 和结束纯乙酸乙酯。收集的主要峰值, 由紫外线吸收在 254 nm 和集中的组合, 相应的分数在一个旋转蒸发器获得纯化产品6c作为一个白色固体。</li>
</ol>

<ol>
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K., Liao, P., Bi, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tandem+O-H+Insertion/[1,3]-Alkyl+Shift+of+Rhodium+Azavinyl+Carbenoids+with+Benzylic+Alcohols:+A+Route+To+Convert+C-OH+Bonds+into+C-C+Bonds.">Tandem O-H Insertion/[1,3]-Alkyl Shift of Rhodium Azavinyl Carbenoids with Benzylic Alcohols: A Route To Convert C-OH Bonds into C-C Bonds.</a> Org. Lett. 18 (19), 4998-5001 (2016).</li><li>Seo, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sequential+Functionalization+of+the+O-H+and+C(sp2)-O+Bonds+of+Tropolones+by+Alkynes+and+N-Sulfonyl+Azides.">Sequential Functionalization of the O-H and C(sp2)-O Bonds of Tropolones by Alkynes and N-Sulfonyl Azides.</a> Adv. Synth. Catal. 358 (7), 1078-1087 (2016).</li><li>Miura, T., Nakamuro, T., Kiraga, K., Murakami, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+stereoselective+synthesis+of+&#945;-amino+aldols+starting+from+terminal+alkynes.">The stereoselective synthesis of &#945;-amino aldols starting from terminal alkynes.</a> Chem. Commun. 50 (72), 10474-10477 (2014).</li><li>Hazen, G. G., Weinstock, L. M., Connell, R., Bollinger, F. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Safer+Diazotransfer+Reagent.">A Safer Diazotransfer Reagent.</a> Synth. Commun. 11 (12), 947-956 (1981).</li><li>Easton, N. R., Bartron, L. R., Meinhofer, F. L., Fish, V. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Some+Substituted+3-Piperidones.">Synthesis of Some Substituted 3-Piperidones.</a> J. Am. Chem. Soc. 75 (9), 2086-2089 (1953).</li><li>Van den Branden, S., Compernolle, F., Hoornaert, G. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+lactam+and+ketone+precursors+of+2,7-substituted+octahydro-pyrrolo[1,2-a]pyrazines+and+octahydro-2H-pyrido[1,2-a]pyrazines.">Synthesis of lactam and ketone precursors of 2,7-substituted octahydro-pyrrolo[1,2-a]pyrazines and octahydro-2H-pyrido[1,2-a]pyrazines.</a> J. Chem. Soc., Perkin Trans 1. 1 (8), 1035-1042 (1992).</li><li>Aszodi, J., Rowlands, D. A., Mauvais, P., Collette, P., Bonnefoy, A., Lampilas, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+and+synthesis+of+bridged+&#947;-lactams+as+analogues+of+&#946;-lactam+antibiotics.">Design and synthesis of bridged &#947;-lactams as analogues of &#946;-lactam antibiotics.</a> Bioorg. Med. Chem. Lett. 14 (10), 2489-2492 (2004).</li><li>D&#8217;hooghe, M., Baele, J., Contreras, J., Boelens, M., De Kimpe, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reduction+of+5-(bromomethyl)-1-pyrrolinium+bromides+to+2-(bromomethyl)pyrrolidines+and+their+transformation+into+piperidin-3-ones+through+an+unprecedented+ring+expansion-oxidation+protocol.">Reduction of 5-(bromomethyl)-1-pyrrolinium bromides to 2-(bromomethyl)pyrrolidines and their transformation into piperidin-3-ones through an unprecedented ring expansion-oxidation protocol.</a> Tetrahedron Lett. 49 (42), 6039-6042 (2008).</li></ol>

作者没有什么可透露的。

三2 a-b可以通过铜 (I)-催化叠氮化-炔烃 [3 + 2] 加 (CuAAC) 以 CuTC 为催化剂清洁地获得。值得注意的是, 在高温下, 三唑2a是最有效的, 通过标准氯仿回流在3h 或加热到100° c, 在微波反应器中15分钟 (注: 时间可能因微波效率的不同而变化);然而, 三唑2b通过室温下的 CuAAC 最有效地制备。因此, 在新的基板上执行本协议时, 必须努力确定此基板相关反应的最佳条件。在微波促进合成的2a中, 必须注意不要在微波中加热100° c 以上的反应, 或超过15分钟, 因为这通常会导致大量的分解。
微波加热的三唑2a与1摩尔的铑 (II) 乙酸二聚体在100° c 氯仿生成N-(2-alkoxyvinyl) 磺胺酰胺 phthalan 3a在高产和纯度。有几次尝试修改这个程序, 但是, 只有微波加热协议取得了良好的效果。例如, 在100° c 的传统油浴中, 通过 submersing 密封的微波瓶来执行反应, 只导致产品的复杂混合物。由于三唑2a和 phthalan 3a合成的两个程序都使用氯仿作为溶剂, 并在100° c 下进行, 因此我们也多次尝试执行一个罐式协议, 以直接从炔烃合成3a 1a在磺叠氮化物、CuTC 和 Rh 的存在下2 (华侨)4在各种条件下, 但没有成功。11
在处理3a时, 避免酸性条件是至关重要的, 因为这会导致快速分解。例如, 当3a通过一个简短的硅胶插头进行纯化时, 可以通过1H 核磁共振波谱数据 (图 4) 来获得纯产品。但是, 在二氧化硅或 non-neutralized CDCl3 (包含微量 HCl/DCl) 上的3a存储超过几分钟后将导致产品的复杂混合 (图 5)。据推测, 此过程是通过在亲核呋喃3a及其相应的亲异构体7之间进行凝结而产生的。值得注意的是, 在使用之前已被 K2CO3中中和的 CDCl3显著地减慢了3a的分解过程, 但并不完全。有趣的是, N-(2-alkoxyvinyl) 磺酰胺 phthalan 3b被发现在轻度酸性, non-neutralized CDCl3至少 3 d 和在存储4周内稳定, 这表明空间位阻和/或电子因素可以用来减弱这个功能群的反应性。
N-(2-Alkoxyvinyl) 磺胺, 如3a作为一个关键的中间体, 当新鲜的准备可以作为独特的前体向 phthalan 和乙胺衍生物。在乙醇或 EtOAc 中, 10 摩尔钯/C 的催化加氢, 在高收率下提供 phthalan 4 , 而对钠双 (2-氧) 铝氢化物进行处理则提供环形打开的乙胺5 (图 2)。在每一个这些减少, 溶剂对反应的效率有重大影响。氢化在甲醇生成的4在类似的纯度, 但显著降低产量。以二乙基醚为主要溶剂时, 只发现氢化铝的还原作用;在呋喃、MTBE、14-二、PhMe 或 CHCl3中尝试此反应时, 很少对任何产品进行观察。
溶解新的准备的3a在含酒精的溶剂中含有催化 TMSCl 提供酮6 a-c在中等到高的收益率。另外, thioketal 6e可以通过使用 3 eq 的辛硫醇来处理3a , 而 hemiketal 6d则是通过在1:1 乙酸和水混合物中搅拌3a产生的。
这种 ketalization 方法的一个显著优势是, 所得到的化合物是一个差异保护的α-氨基酮, 一个经常不稳定的化合物, 每当一个基本胺和 enolizable 酮同时存在。29,30,31,32此外, 如图 9所示, 差异保护可提供在单独的正交操作中操作受保护胺或酮的策略优势。
在未来, 我们希望这些协议可以用于合成新的, 生物活性化合物轴承特许乙胺下部结构和/或 phthalan 脚手架。此外, 我们还演示了N-(2-alkoxyvinyl) 磺胺作为多功能功能组的效用。因此, 进一步调查这不足 synthon 在有价值的合成转变是值得的。

铑 (II)-azavinyl carbenoids 最近出现了作为一个异常地多才多艺的反应中间 en 到许多可贵的产品的路线。1,2,3,4,5,6,7,8,9,10特别地, 这些中间体的许多新颖的用途为生产杂10为化学家提供了新的和高效率的综合战略。为此, 我们集团发起了一项新的 phthalans11合成协议的开发, 这将利用最近在和 oxygen-based 核内分子内添加的进展到 Rh (II)-azavinyl carbenoids从N-sulfonyl-1,2,3-triazoles 派生的。12,13,14,15,16,17我们的方法具有一个简单的 two-step 协议, 用于将终端炔烃如1转换为N-sulfonyl-1,2,3-triazoles 2 , 并带有一个下垂的酒精 (图 1)。随后, Rh (II)-催化脱/13 OH 插入级联从2提供 phthalans 3具有反应性的N(2-alkoxyvinyl) 磺胺类官能团。
由于n-(2-alkoxyvinyl) 磺胺类基团是一种潜在的多用途, 但相对 (的n-和O-包含 synthon,16,17,18,19,20,21,22,23,24,25,26,27在各种条件下 (图 2), 我们对其熔融烯-醚/烯-磺酰胺系统的反应性感兴趣。在筛选各种还原协议后, 确定了两种方法, 它们导致了稳定的 phthalan 和/或包含乙胺的产品 (图 2, 3 → 4/5)。首先, 它被发现, 标准氢化的N-(2-alkoxyvinyl) 磺酰胺的3a与催化钯碳 (Pd/c) 有选择地减少 c = c 键屈服 phthalan 4。另外, 在乙醚/甲苯中使用钠双 (2-氧) 铝氢化物处理的3a提供了唯一替代的乙胺导数5。我们认为, 这两种转换都是有价值的, 因为它们导致具有潜在生物活性的产品类别, 包括嵌入乙胺产生的活性属性, 而在4的情况下, 金属螯合通过面向cis的N和O-原子。
在调查酸性促进的添加物以利用富含电子的 c = c 键的3a时, 发现在酒精或硫醇存在的情况下, 用催化的三甲基硅基氯化物处理此化合物, 产生了酮6 c和分别 thioketal 6e, 同时保持双 phthalan 框架的完整性。另外, 在1:1 乙酸/水溶液中搅拌3a会产生稳定的 hemiketal 6d。

<table><tbody><tr><td>2-Ethynylbenzyl alcohol, 95%</td><td>Sigma Aldrich</td><td>520039</td><td></td></tr><tr><td>Copper (I) thiophene-2-carboxylate</td><td>Sigma Aldrich</td><td>682500</td><td></td></tr><tr><td>Chloroform, &amp;ge;99%</td><td>Sigma Aldrich</td><td>372978</td><td></td></tr><tr><td>Toluenesulfonylazide, 99.24%</td><td>Chem-Impex International</td><td>26107</td><td>Potentially explosive</td></tr><tr><td>Dichloromethane, &amp;ge;99.5%</td><td>Sigma Aldrich</td><td>320269</td><td></td></tr><tr><td>Rhodium (II) acetate dimer, 99%</td><td>Strem Chemicals</td><td>45-1730</td><td></td></tr><tr><td>Silica Gel, 32-63, 60A</td><td>MP Biomedicals Inc.</td><td>2826</td><td>For silica gel plugs</td></tr><tr><td>Hexanes</td><td>Sigma Aldrich</td><td>178918</td><td></td></tr><tr><td>Ethyl acetate</td><td>Sigma Aldrich</td><td>439169</td><td></td></tr><tr><td>Chlorofom-D</td><td>Sigma Aldrich</td><td>151823</td><td></td></tr><tr><td>Ethylene glycol</td><td>Sigma Aldrich</td><td>293237</td><td></td></tr><tr><td>Chlorotrimethylsilane, 98%</td><td>Acros</td><td>11012</td><td></td></tr><tr><td>Sodium bicarbonate</td><td>Sigma Aldrich</td><td>S6014</td><td>Dissolved in deionized water to prepare a saturated aqueous solution</td></tr><tr><td>Sodium sulfate</td><td>Fisher Scientific</td><td>S429</td><td></td></tr><tr><td>Ethyl alcohol, absolute - 200 proof</td><td>Aaper Alcohol and Chemical Co.</td><td>82304</td><td></td></tr><tr><td>10 wt% Palladium on carbon</td><td>Sigma Aldrich</td><td>520888</td><td>Can ignite in the presence of air, hydrogen gas, and/or a flammable solvent</td></tr><tr><td>Hydrogen gas</td><td>Praxair</td><td>UN1049</td><td></td></tr><tr><td>Diethyl ether</td><td>Sigma Aldrich</td><td>309966</td><td></td></tr><tr><td>60 wt% sodium bis(2-methoxyethoxy)aluminum hydride solution in toluene</td><td>Sigma Aldrich</td><td>196193</td><td>Reacts violently with water</td></tr><tr><td>Methanol</td><td>Sigma Aldrich</td><td>34966</td><td></td></tr><tr><td>Ammonium chloride</td><td>Fisher Scientific</td><td>A661</td><td>Dissolved in deionized water to prepare a saturated aqueous solution</td></tr><tr><td>Hydrochloric acid, 37%</td><td>Sigma Aldrich</td><td>258148</td><td>Dissolved in deionized water to prepare a 1M solution</td></tr><tr><td>Sodium Chloride</td><td>Sigma Aldrich</td><td>S25541</td><td>Dissolved in deionized water to prepare a saturated aqueous solution</td></tr><tr><td>2-5 mL Microwave vials</td><td>Biotage</td><td>355630</td><td></td></tr><tr><td>Microwave vial caps</td><td>Biotage</td><td>352298</td><td></td></tr><tr><td>RediSep Rf Gold Normal Phase, Silica Columns, 20 &amp;ndash; 40 micron</td><td>Teledyne Isco</td><td>69-2203-345</td><td>For column chromatography</td></tr><tr><td>Balloons</td><td>CTI Industries Corp.</td><td>912100</td><td>For hydrogenation</td></tr><tr><td>Biotage Initiator+ Microwave Reactor</td><td>Biotage</td><td>356007</td><td></td></tr></tbody></table>

preparation of n-(2-alkoxyvinyl)sulfonamides from n-tosyl-1,2,3-triazoles and subsequent conversion to substituted phthalans and phenethylamines

分解的N-tosyl-1,2,3-triazoles 与铑 (II) 乙酸二聚体在醇的存在形式综合地多才多艺的N-(2-alkoxyvinyl) 磺胺, 在各种各样的情况下起反应到负担得起有用的n和包含化合物的O。酸催化添加醇或硫到N-(2-alkoxyvinyl) 含有磺胺类的 phthalans, 分别提供了酮和 thioketals 的通道。选择性还原乙烯基在N-(2-alkoxyvinyl) 含有磺酰胺的 phthalans 通过加氢生成相应的 phthalan 在良好的产量, 而减少与钠双 (2-氧) aluminumhydride 产生环形开启的乙胺模拟。由于N-(2-alkoxyvinyl) 磺酰胺官能团是综合通用的, 但通常作用不稳定, 因此该协议强调在准备、处理和反应这些关键基板的几个有用转换.

本研究的所有化合物都以1H 和13C 核磁共振波谱和电喷雾质谱 (ESI) 为特征, 以确认产品结构并评估纯度。本节描述了代表性化合物的关键数据。
光谱数据与2a (图 3) 的三唑结构有很好的一致性。在2a的1H 核磁共振谱中, 三唑的特征 C5 质子出现在 8.45 ppm, 为1H 的单线态积分。通过 ESI-MS 获得的质量谱一般显示了 MH + 峰值和与氮损失对应的 M-N2峰值。
N-(2-alkoxyvinyl) 磺酰胺 phthalan 的合成3a通过我们的协议可靠地交付产品和 #62; 90% 产量, 但是, 关键参数 (如时间、温度和加热方法) 的重大偏差显著影响反应的效率 (韦迪), 因此, 光谱数据的质量。图 4a描述了一个成功的实验后的1H 核磁共振频谱的纯3a 。值得注意的是, 三唑 C5 质子峰的缺席约 8.5 ppm (cf.图 3) 和两个双峰的外观分别在6.07 和6.25 对应的乙烯基和 NH 质子。在13C 核磁共振谱的3a, 一个关键的共振是观察到 94.9 ppm, 对应于双键乙烯基碳。为进行比较,图 5说明了 CDCl3中快速退化导致的3a分解产品的1H 核磁共振频谱。
图 6和图 7显示1H/13C 核磁共振和质谱, 它们分别与还原产品的结构 ( 4和5) 很好地一致。4的1H 核磁共振谱, 它保持了双 phthalan 子结构, 显示了对应于 diastereotopic 亚甲基质子3.49 和 3.14 ppm 的关键信号。Contrastingly, 1H 核磁共振谱乙胺5显示了相同的亚甲, 作为一个简单的四重奏在 3.27 ppm, 由于自由旋转的环打开的产品导致了一阶分裂模式。
对于化合物6 a-e, 一个特征的13c 核磁共振信号对应于酮, hemiketal 或 thioketal 碳被发现之间 95-110 ppm, 如峰值在 110.0 ppm 在13C 核磁共振谱中观察到6c (图 8)。此外, 由 ESI-MS 获得的质谱通常显示一个相对较小的 MH + 峰值, 以及更大的 M rx 消除片段峰值 (RX = 对应的烷或 thioalkyl 组6)。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56848/56848fig1.jpg"> 
图 1.N-tosyl-1,2,3-triazoles 2通过 Cu (一)-催化叠氮化物-炔烃 [3 + 2] 加和随后转换为N-(2-alkoxyvinyl) 磺胺酰胺 phthalans 3通过 Rh (II)-催化醇环.<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig1large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56848/56848fig2.jpg"> 
图 2.N的差分反应性-(2-alkoxyvinyl) 磺酰胺 phthalan 3a: 通过钯催化加氢转化为还原 phthalan 4 , 转换为乙胺5通过铝氢化物还原, 并转换为酮6 a-c, hemiketal 6d, 和 thioketal 6e通过酸促进添加醇, 水和硫醇, 分别。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig2large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56848/56848fig3.jpg"> 
图 3.三唑2a的光谱数据: (a) 1H 核磁共振谱;(b) 13C 核磁共振谱;和 (c) 质谱。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig3large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56848/56848fig4.jpg"> 
图 4.光谱数据为N-(2-alkoxyvinyl) 磺酰胺 phthalan 3a: (a) 1H 核磁共振谱;(b) 13C 核磁共振谱 (小峰值是由于 CDCl3) 迅速退化而产生的分解产物;和 (c) 质谱。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig4large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56848/56848fig5.jpg"> 
图 5.(a) 1H 核磁共振谱的3a和分解产品在存储后 CDCl3为1h。(b) 3a 的虚拟分解机制<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig5large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56848/56848fig6.jpg"> 
图 6.用于减少 phthalan 的光谱数据4: (a) 1H 核磁共振谱;(b) 13C 核磁共振谱;和 (c) 质谱。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig6large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56848/56848fig7.jpg"> 
图7。乙胺5的光谱数据: (a) 1H 核磁共振谱;(b) 13C 核磁共振谱;和 (c) 质谱。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig7large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/56848/56848fig8.jpg"> 
图 8.酮6c的光谱数据: (a) 1H 核磁共振谱;(b) 13C 核磁共振谱;和 (c) 质谱。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig8large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/56848/56848fig9.jpg"> 
图 9。对复合6进行操作的策略性考虑, 一个差异保护的α-aminoketone。<a href="//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56848/56848fig9large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>

Watch this Scientific Journal Video about Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines at JoVE.com

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

准备n-(2-alkoxyvinyl) 磺胺从n-tosyl-1,2,3-triazoles 和随后转换为取代 Phthalans 和 Phenethylamines

本文详细介绍了合成N-(2-alkoxyvinyl) 磺胺以及随后转换为 phthalan 和乙胺衍生物的典型实验过程。

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile ...

preparation-n-2-alkoxyvinyl-sulfonamides-from-n-tosyl-123-triazoles

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Unit 1

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Amines

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9.6K 次观看.  Hamilton College. 本文详细介绍了合成N-(2-alkoxyvinyl) 磺胺以及随后转换为 phthalan 和乙胺衍生物的典型实验过程。

视频: Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Modification and Functionalization of the Guanidine Group by Tailor-made Precursors

The guanidine group is one of the most important pharmacophoric groups in medicinal chemistry. The only amino acid carrying a guanidine group is arginine. In this article, an easy method for the modification of the guanidine group in peptidic ligands is provided, with an example of RGD-binding integrin ligands. It was recently demonstrated that the distinct modification of the guanidine group in these ligands allows for the selective modulation of the subtype (e.g., between the subtypes &#945;v and &#945;5). Moreover, a formerly unknown strategy for the functionalization via the guanidine group was demonstrated, and the synthetic approach is reviewed in this document. The modifications described here involve terminally (N&#969;) alkylated and acetylated guanidine groups. For the synthesis, tailor-made precursor molecules are synthesized, which are then subjected to a reaction with an orthogonally deprotected amine to transfer the pre-modified guanidine group. For the synthesis of alkylated guanidines, precursors based on N,N&#8242;-Di-Boc-1H-pyrazole-1-carboxamidine are used to synthesize acylated compounds, the precursor of choice being a correspondingly acylated derivative of N-Boc-S-methylisothiourea, which can be obtained in one- and two-step reactions.

A protocol for the synthesis of alkyl-modified guanidines based on the use of the corresponding precursors is presented.

修改和胍集团的官能通过量身定制的前兆

The guanidine group is one of the most important pharmacophoric groups in medicinal chemistry. The only amino acid carrying a guanidine group is arginine. ...

科研

生物化学

Facile Preparation of 4-Substituted Quinazoline Derivatives

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted 2-aminobenzophenones and thiourea in the presence of dimethyl sulfoxide (DMSO). This is a unique complementary reaction system in which thiourea undergoes thermal decomposition to form carbodiimide and hydrogen sulfide, where the former reacts with 2-aminobenzophenone to form 4-phenylquinazolin-2(1H)-imine intermediate, whilst hydrogen sulfide reacts with DMSO to give methanethiol or other sulfur-containing molecule which then functions as a complementary reducing agent to reduce 4-phenylquinazolin-2(1H)-imine intermediate into 4-phenyl-1,2-dihydroquinazolin-2-amine. Subsequently, the elimination of ammonia from 4-phenyl-1,2-dihydroquinazolin-2-amine affords substituted quinazoline derivative. This reaction usually gives quinazoline derivative as a single product arising from 2-aminobenzophenone as monitored by GC/MS analysis, along with small amount of sulfur-containing molecules such as dimethyl disulfide, dimethyl trisulfide, etc. The reaction usually completes in 4-6 hr at 160 &#186;C in small scale but may last over 24 hr when carried out in large scale. The reaction product can be easily purified by means of washing off DMSO with water followed by column chromatography or thin layer chromatography.

A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

的4-取代喹唑啉衍生物简便制备

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted ...

化学

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

协议的合成<em&gt;邻</em&gt; -trifluoromethoxylated苯胺类化合物

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the aziridine ring. The utility of bicyclic aziridinium ions, specifically 1-azoniabicyclo[3.1.0]hexane and 1-azoniabicyclo[4.1.0]heptane tosylate highlighted in the aziridine ring openings by the nucleophile with the release of the ring strain to yield the corresponding ring-expanded azaheterocycles such as pyrrolidine, piperidine and azepane with diverse substituents on the ring in regio- and stereospecific manner. Herein, we report a simple and convenient method for the preparation of the stable 1-azabicyclo[4.1.0]heptane tosylate followed by selective ring opening via a nucleophilic attack either at the bridge or at the bridgehead carbon to yield piperidine and azepane rings, respectively. This synthetic strategy allowed us to prepare biologically active natural products containing piperidine and azepane motif including sedamine, allosedamine, fagomine and balanol in highly efficient manner.

Bicyclic aziridinium ions such as 1-azoniabicyclo[4.1.0]heptane tosylate were generated from 2-[4-tolenesulfonyloxybutyl]aziridine, which was utilized for the preparation of substituted piperidines and azepanes via regio- and stereospecific ring-expansion with various nucleophiles. This highly efficient protocol allowed us to prepare diverse azaheterocycles including natural products such as fagomine, febrifugine analogue and balanol.

稳定笼 Aziridinium 离子的制备及其开环 Azaheterocycles 的合成

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the ...

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

&#945;-Functionalization of ketones via umpolung of enolates by hypervalent iodine reagents is an important concept in synthetic organic chemistry. Recently, we have developed a two-step strategy for ketone enolate umpolung that has enabled the development of methods for chlorination, azidation, and amination using azoles. In addition, we have developed C-C bond&#8211;forming arylation and allylation reactions. At the heart of these methods is the preparation of the intermediate and highly reactive enolonium species prior to addition of a reactive nucleophile. This strategy is thus reminiscent of the preparation and use of metal enolates in classical synthetic chemistry. This strategy allows the use of nucleophiles that would otherwise be incompatible with the strongly oxidizing hypervalent iodine reagents. In this paper we present a detailed protocol for chlorination, azidation, N-heteroarylation, arylation, and allylation. The products include motifs prevalent in medicinally active products. This article will greatly assist others in using these methods.

A two step one-pot protocol for the umpolung of ketone enolates to enolonium species and addition of a nucleophile to the &#945;-position is described. Nucleophiles include chloride, azide, azoles, allyl-silanes, and aromatic compounds.

Enolonium 种极性转换酮功能化的两步协议

&#945;-Functionalization of ketones via umpolung of enolates by hypervalent iodine reagents is an important concept in synthetic organic chemistry. ...

Easy Access to Aliphatic Sulfonamides using Sulfamoyl Chlorides Under Visible Light Activation

Sulfonamides are prevalent motifs in marketed drugs and natural products. Their synthesis represents a great interest to the pharmaceutical industry, due to their unique biological properties. Recently, several methods for the synthesis of aryl sulfonamides have been developed, but little effort has focused on developing one-step methodologies to access sulfonamides flanked by two alkyl groups. This protocol describes a practical and facile method for the net hydrosulfamoylation of electron-deficient alkenes using sulfamoyl chlorides as radical precursors under blue-light activation. This practical and cost-effective methodology is performed in the presence of the metal-free photocatalyst Eosin Y and uses light as a clean and traceless energy source. The procedure is scalable, displays a broad functional group tolerance, and can be applied for late-stage functionalization. All reagents used in this protocol are commercially available. Simple reaction set-up, the absence of work-up and easy purification, demonstrate the convenience of this protocol. The reaction is best applied to electron-deficient alkenes.

Presented here is a protocol for the easy synthesis of aliphatic sulfonamides using sulfamoyl chlorides, (TMS)3SiH and Eosin Y under blue-light irradiation.

Sulfonamides are prevalent motifs in marketed drugs and natural products. Their synthesis represents a great interest to the pharmaceutical industry, due ...

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine

Nitrogen-containing heterocycle aziridines are synthetically very valuable for the preparation of azacyclic and acyclic molecules. However, it is very difficult and laborious to make aziridines in optically pure forms on a large scale to apply asymmetric synthesis of aza compounds. Fortunately, we successfully achieved both enantiomers (2R)- and (2S)-aziridine-2-carboxylates with the electron-donating &#945;-methylbenzyl group at the ring nitrogen as non-activated aziridines. These starting aziridines have two distinct functional groups-highly reactive three-membered ring and versatile carboxylate. They are applicable in ring-opening or ring-transformation with aziridine and in functional group transformation to others from carboxylate. Both of these enantiomers were utilized in the preparation of biologically important amino acyclic and/or aza-heterocyclic compounds in an asymmetric manner. Specifically, this report describes the first expedient asymmetric synthesis of both enantiomers of 5, 6-dihydrouracil-type marine natural products biemamide B and D as potential TGF-&#946; inhibitors. This synthesis consisted of regio- and the stereoselective ring-opening reaction of aziridine-2-carboxylate and subsequent formation of 4-aminoteterahydropyrimidine-2,4-dione. One more example in this protocol dealt a highly stereoselective Mukaiyama reaction of aziridine-2-carboxylate and silyl enol ether, following intramolecular aziridine ring-opening to provide easy and facile access to (-)-epiallo-isomuscarine.

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine

In this study, we prepare both enantiomers of aziridine-2-carboxylate, which are used in the asymmetric synthesis of alkaloids, including biemamide B and D, and (-)-epiallo-isomuscarine.

对映草非活化氮丙啶的制备及比咪咪唑B、D和 表皮异毒羯碱的合成

Nitrogen-containing heterocycle aziridines are synthetically very valuable for the preparation of azacyclic and acyclic molecules. However, it is very ...

<meta charset="utf8"></head><body>噻吩磺酰胺在群体感应抑制中的生物学评价

Synthesis and Assay of Vibrio Quorum Sensing Inhibitors

Bacteria detect local population numbers using quorum sensing, a method of cell-cell communication broadly utilized to control bacterial behaviors. In Vibrio species, the master quorum sensing regulators LuxR/HapR control hundreds of quorum sensing genes, many of which influence virulence, metabolism, motility, and more. Thiophenesulfonamides are potent inhibitors of LuxR/HapR that bind the ligand pocket in these transcription factors and block downstream quorum sensing gene expression. This class of compounds served as the basis for the development of a set of simple, robust, and educational procedures for college students to assimilate their chemistry and biology skills using a CURE model: course-based undergraduate research experience. Optimized protocols are described that comprise three learning stages in an iterative and multi-disciplinary platform to engage students in a year-long CURE: (1) design and synthesize new small molecule inhibitors based on the thiophenesulfonamide core, (2) use structural modeling to predict binding affinity to the target, and (3) assay the compounds for efficacy in microbiological assays against specific Vibrio LuxR/HapR proteins. The described reporter assay performed in E. coli successfully predicts the efficacy of the compounds against target proteins in the native Vibrio species.

<meta charset="utf8"></head><body>作者聚焦：推进治疗人类和水生生物弧菌病的疗法

Thiophenesulfonamide compounds are potent and specific inhibitors of Vibrio quorum sensing regulators LuxR/HapR that block their activity in vivo, thus preventing transcription of genes for virulence, motility, and biofilms. This protocol details how these compounds are synthesized, modeled in silico, and assayed in vivo for activity against LuxR/HapR.

弧菌群体感应抑制剂的合成和测定

Bacteria detect local population numbers using quorum sensing, a method of cell-cell communication broadly utilized to control bacterial behaviors. In ...

准备n-(2-alkoxyvinyl) 磺胺从n-tosyl-1,2,3-triazoles 和随后转换为取代 Phthalans 和 Phenethylamines

摘要

探索更多视频

此视频中的章节

修改和胍集团的官能通过量身定制的前兆

的4-取代喹唑啉衍生物简便制备

协议的合成

稳定笼 Aziridinium 离子的制备及其开环 Azaheterocycles 的合成

Enolonium 种极性转换酮功能化的两步协议

Easy Access to Aliphatic Sulfonamides using Sulfamoyl Chlorides Under Visible Light Activation

对映草非活化氮丙啶的制备及比咪咪唑B、D和表皮异毒羯碱的合成

弧菌群体感应抑制剂的合成和测定

弧菌群体感应抑制剂的合成和测定

弧菌群体感应抑制剂的合成和测定

准备n-(2-alkoxyvinyl) 磺胺从n-tosyl-1,2,3-triazoles 和随后转换为取代 Phthalans 和 Phenethylamines

摘要

探索更多视频

此视频中的章节

修改和胍集团的官能通过量身定制的前兆

的4-取代喹唑啉衍生物简便制备

协议的合成

稳定笼 Aziridinium 离子的制备及其开环 Azaheterocycles 的合成

Enolonium 种极性转换酮功能化的两步协议

Easy Access to Aliphatic Sulfonamides using Sulfamoyl Chlorides Under Visible Light Activation

对映草非活化氮丙啶的制备及比咪咪唑B、D和 表皮异毒羯碱的合成

弧菌群体感应抑制剂的合成和测定

弧菌群体感应抑制剂的合成和测定

弧菌群体感应抑制剂的合成和测定

对映草非活化氮丙啶的制备及比咪咪唑B、D和表皮异毒羯碱的合成