金催化联烯胺与烯基叠氮的加成反应构建α-烯丙基酮化合物.pdf

do1.10.2024.01.006Vol.50 No.1Journal of SouthvstMinzuUniversity(Natural Science EditionATPC第50 卷第1期Jan.20242024年1月西南民族大自然科学版）金催化联烯胺与烯基叠氮的加成反应构建-烯丙基酮化合物杨岚，古文,王甜密，李肖肖,赵志刚（西南民族大学化学与环境学院，四川成都6 10 0 41）摘要：烯基叠氮是一类重要的有机合成中间体，被广泛应用于含氮杂环化合物的合成中，但将其应用于联烯胺的加成反应少见报道.利用金催化活化联烯胺形成的烯丙基正离子中间体与烯丙基叠氮化合物发生加成反应，进一步发生水解得到9个-烯丙基酮衍生物，所得产物均通过红外、核磁共振以及高分辨质谱进行确认，其中，对化合物3i进行了X-单晶衍射，确定了其结构.该反应利用烯基叠氮作为亲核试剂，实现了联烯胺与其加成反应，丰富了联烯胺的反应类型.关键词：金催化；联烯胺；烯基叠氮；加成反应；-烯丙基酮中图分类号：0 6 2 1.2 51文献标志码：A文章编号:2 0 95-42 7 1(2 0 2 4)0 1-0 0 44-0 8Synthesis of-allyl ketones via gold-catalyzed coupling ofallenamides with vinyl azidesYANG Lan,GU Wen,WANG Tian-mi,LI Xiao-xiao,ZHAO Zhi-gang(School of Chemistry&Environment,Southwest Minzu University,Chengdu 610041,China)Abstract:Vinyl azides are versatile building blocks which are widely applied to the synthesis of nitrogen-containingheterocycles.However,there is no report on the coupling reaction of allenamides with vinyl azides.This paper reported an effi-cient addition reaction of vinyl azides with allyl cationic intermediate formed by gold-catalyzed activation of allenamides,whichsubsequently hydrolyzed to obtain 9 of-allyl ketones.All the products were characterized by IR,NMR and HRMS.Moreover,the precise configuration of-allyl ketones was unambiguously confirmed by single-crystal X-ray analysis of 3i.This method en-riched the study of allenamides via using vinyl azides as the nucleophilic reagents to the addition reactions of allenamides.Keywords:gold catalysis;allenamides;vinyl azides;addition reaction;-allyl ketone烯丙基骨架结构广泛存在于天然产物分子、药物分子以及生物活性分子中.因其特殊的分子结构,该类化合物也是一类非常重要的合成中间体1-3.近年来，化学家们对-烯丙基酮化合物的合成表现出了浓厚的兴趣.目前报道的合成-烯丙基酮化合物的常用方法是通过在酮类底物的位进行烯丙基取代反应，如钯/铱催化酮或烯醇与烯丙基碳酸酯的烯丙基烷基化反应46 ，钯催化烯丙基烯醇碳酸酯的脱羧反应7-10 ,钉催化乙酰基碳酸烯丙基酯的脱羧反应1,12 1,钯催化烯基碳酸酯与烯丙基醇的加成反应13.14,以及钯/锌催化的烯胺的烯丙基烷基化反应等15,16 .这类反应所用的烯丙基源大多带有离去基团,如烯丙基卤化物、烯丙基醇、烯丙基酯等,反应过程中会产生当量的副产物，原子经济性较差.收稿日期：2 0 2 3-0 6-2 5通信作者：李肖肖（198 6-），女，高级实验师，博士.研究方向：有机合成方法学.E-mail:；赵志刚（196 3-），男，教授，博士研究方向：有机合成方法学.E-mail：z z g 6 312 9 16 3.c o m基金项目：西南民族大学中央高校基本科研业务费专项资金项目（No.ZYN2022017）45期第杨岚催化联烯胺与烯基叠氮的加成反应构建义-烯丙基酮化合物近年来，不饱和烃如联烯、炔烃和1,3-二烯，被广泛用作烯丙基试剂17-2 1。相比传统的带有离去基团的烯丙基试剂，不饱和烃作为烯丙基试剂具有原子经济性高、无副产物产生等诸多优点.其中，联烯胺作为富电子联烯，近年来被广泛应用于有机合成中2 2-2 7 .在路易斯酸的作用下，联烯胺通常作为亲电的元-烯丙基前体与不同类型的亲核试剂发生反应，可以区域选择性地形成烯基化产物或烯丙基化的产物.烯基叠氮化合物是一类常用的氮杂偶极子，用于构建杂环类化合物2 8-3.最近，化学家们发现烯基叠氮能够用作碳亲核试剂,构建-烯丙基酰胺和腈化合物3440 .如新加坡南洋理工的Shunsuke教授于2 0 15年报道了三氟甲磺酰胺催化的烯基叠氮与醇的亲核加成反应合成一系列酰胺类化合物；浙江大学崔孙良老师于2 0 17 年报道了BF,-Et,O促进的对亚甲基苯醌与烯基叠氮的反应，依次发生亲核加成反应及重排反应，得到相应的酰胺及腈化合物.基于此，我们设想以乙烯基叠氮作为亲核试剂，实现金催化联烯胺与乙烯基叠氮的加成反应，构建-烯丙基酮类化合物，如图1所示，金催化剂作为酸活化联烯胺形成金络合的烯丙基碳正离子,接着,烯基叠氮作为亲核试剂进攻烯基金碳正离子形成烯基金叠氮中间体，最后在水的作用下发生水解得到目标产物.ORNAu catalystRNArTsArN3H2O,solventTsN2NH20RArTsAu图1金催化联烯胺与烯基叠氮的加成反应研究Scheme 1Gold-catalyzed coupling of allenamides with vinyl azides1实验部分1.1仪器和试剂WRS-1B数字显示熔点仪（温度未校正）；Agilent400MHz核磁共振仪（内标为TMS,溶剂为CDCl）；Thermo Scientific LTQ Orbitrap XL 型质谱仪;PERKIN-ELMER1700型傅里叶变换红外光谱仪（KBr压片）.试验中所有反应试剂及溶剂均为化学纯或分析纯，1.2实验结果与讨论1.2.1最优反应条件筛选以苯基取代的联烯胺1a及苯基取代的烯基叠氮2a为模板底物，对该反应的最优条件进行了筛选优化，分别从催化剂、催化剂助剂、溶剂、温度及投料比进行了筛选，实验结果如表1所示.首先，以Ph,PAuCl为催化剂，对辅助催化剂进行了筛选，实验结果表明在AgSbF。为辅助催化剂时,反应效果较好，可以得到51%的收率.接着，以AgSbF。为辅助催化剂,对金催化剂进行了简单的筛选发现,Ph,PAuCl为最优催化剂.以Ph,PAuCIVAgSbF。为催化体系，对溶剂进行了简单优化，实验结果表明THF为最优溶剂.接着，对反应的投料比进行了优化，结果表明降低烯基叠氮的用量,产率有所降低.最后将反应温度降低发现，在-2时，产率可以提高至57%.最终确定的反应条件为：在2 C下，以THF为溶剂，以Ph,PAuCIVAgSbF。（5mo l%）为催化体系，联烯胺和烯基叠氮的比例为1:2，反应可以达到57%的收率.1.2.2底物拓展在最优条件下，对反应的底物进行了拓展研究，实验结果如表2 所示.4-甲基-苯基联烯胺能很好地参与反应，以52%的产率得到目标产物3b.接着考察了对位含有卤素取代基的苯胺联烯，实验结果表明,4-氟-苯基联烯胺、4-氯-苯基联烯胺及4-溴-苯基联烯胺都能以中等的产率得到目标产物.2-甲基及2,4,6-三甲基-苯胺联烯也适用于该反应，分别以47%及54%的产率得到目标产物3f及3g.4-氟-苄基联烯胺也能以42%的产率得到目标产物.以4-溴苯胺联烯及4-溴苯基乙烯叠氮为底物，也能以48%的产率得到目标产物3i.对产物3i进行了x-ray单晶衍射，确定了其结构，如图2 所示.46第50 卷西南民族大自然科学版）表1反应条件优化 bTable 1Screening of optimal conditionsa,bPhcatalystNPh+TsPhN3solvent,TocPhTs1a2a3aEntryCatalyst(%)SolventTemp.Time(h)Yield(%)1Ph,PAuCI/AgSbF(5)THF2524512Ph,PAuCI/AgBF4(5)THF2527353Ph,PAuCI/AgOTf(5)THF2525444Ph,PAuCIV/AgNTf,(5)THF2527365Ph,PAuCI/AgCO,(5)THF2572166AuCl3/AgSbF(5)THF2572207JohnPhos AuCl/AgSbF6(5)THF2548trace8Ph,PAuCl/AgSbF(5)DCM250.5169Ph,PAuCl/AgSbF,(5)EA250.51810Ph,PAuCI/AgSbF(5)xylene250.54011Ph,PAuCI/AgSbF(5)acetone2534912Ph,PAuCIV/AgSbF,(5)isopropanol2531713Ph,PAuCIV/AgSbF,(5)CHCl325242814cPh,PAuC/AgSbF,(5)THF25273515Ph,PAuCV/AgSbF,(5)THF40273516Ph,PAuCl/AgSbF,(5)THF-2275717Ph,PAuCVAgSbF(5)THF-102440a除非另有说明，所有反应均在空气中进行，0.1mmol的1a和0.2 mmol的2 a溶解在2 mL溶剂中.b分离产率。2 a的当量为0.1mmol.表2反应底物拓展Table 2Scope of substrates a,hRPh3PAuCI/AgSbF(5mol%)RArN3THF,-2 CArTsTs123MeOTsTsTs3a,57%3b,52%3c,51%BTsTsMeTs3d,41%3e,39%3f,47%MeMeBTsMeTsTsBr3g,54%3h,42%3i,48%反应条件：1（0.1mmol）;2（0.2 mmo l）,T H F（2 mL）.b 分离产率，期47第杨岚，催化联烯胺与烯基叠氮的加成反应构建-烯丙基酮化合物1.2.3可能的反应机理根据实验结果及相关文献报道39，本反应的可能机理如图3所示：首先，联烯胺在金催化剂的作用下形成金络合的烯丙基正离子中间体IntI,接着被烯基叠氮发生亲核进攻,得到中间体IntI,最后发生水解得到目标产物并离去金催化剂完成催化循环.CHBrNS图2 3i的X-ray单晶衍射图Fig.2X-ray structure of 3iN2NPhAu2aPhPNNTsTs Au1aIntIN2PhPhNPhNPhTsTs AuAu3aInt Il图3可能的反应机理Scheme 3Proposed mechanism2化合物数据(E)-4-methyl-N-(5-oxo-5-phenylpent-1-en-1-yl)-N-phenylbenzenesulfonamide(3a)Yellow oil,yield 57%;IR（K Br）（c m):16 93,1364,1209,960,666,580.H NMR(400 MHz,CDCl,)8 7.94-7.79(m,2H,Ar-H),7.50(d,J=7.7 Hz,3H,Ar-H),7.40(t,J=7.6 Hz,2H,Ar-H),7.357.26(m,3H,Ar-H),7.22(d,J=8.0 Hz,2H,Ar-H),7.00(d,J=13.9 Hz,1H,=CH),6.95-6.83(m,2H,Ar-H),4.42（d t,J=14.3,7.3H z,1H,=CH),2.90(t,J=7.3 Hz,2H,-CO-CH2-),2.39(s,48第50 卷西南民族大自然科学版）3H,Ar-CH3),2.365（d,J=7.2 H z,2 H,=C H-CH2-).13C NMR（10 0 M H z，CD Cl,）199.31,143.79,136.84，136.7 2，135.8 2,133.0 2，130.11,129.75，12 9.57，12 9.39，12 8.8 5，12 8.57，12 7.98,127.44,110.84,38.75,24.77,21.59.HRMS（ESI)m/z calcd for C24H24 NO,S*(M+H)*406.1477,found406.1469.MeTs(E)-4-methyl-N-(5-oxo-5-phenylpent-1-en-1-yl)-N-(p-tolyl)benzenesulfonamide(3b)Yellow oil,yield 52%;IR（K Br）（c m):16 93,1567,1361,1168,817,591.HNMR（40 0 M H z,CDCl,)8 7.86(d,J=7.6 Hz,2H,Ar-H),7.54(dd,J=20.6,7.6 Hz,3H,Ar-H),7.41(t,J=7.6 Hz,2H,Ar-H),7.23(d,J=6.4 Hz,4H,Ar-H),7.12-6.94(m,2H,Ar-H,=CH),6.50(d,J=7.9 Hz,1H,Ar-H),4.21(dt,J=14.3,7.3 Hz,1H,=CH),2.90(t,J=7.3 Hz,2H,-CO-CH,-),2.41（s,3H,A r-C H,),2.37(t,J=7.3 Hz,2H,=CH-CH2-),2.13(s,3H,Ar-CH,）.13CNM R（10 0 M H z,CD Cl,）199.36,143.72,139.21，136.8 6，136.56，135.13，133.0 1,131.60,129.62,129.48,129.11,128.56，12 7.98,126.62,109.69,38.89,24.72,21.60,17.84.HRMS(ESI)m/z calcd for C2s H2s NO,SNa*（M +Na)+442.1453,found 442.1446.Ts（E)-N-(4-f l u o r o p h e n y l )-4-me t h y l-N-(5-o x o-5-phenylpent-1-en-1-yl)benzenesulfonamide(3c)Light yellow powder,yield 51%,m.p.75-76;IR(KBr）（c m)：16 8 3,150 7,117 1,931,8 16,591.HNMR（40 0 M H z,CD Cl,）7.93（d,J=7.7 H z,2 H,Ar-H),7.57(dd,J=14.9,7.6 Hz,3H,Ar-H),7.49(t,J=7.6 Hz,2H,Ar-H),7.36-7.25(m,2H,Ar-H),7.11-6.99(m,3H,Ar-H,=CH),6.93(dd,J=8.7,4.9 Hz,2H,Ar-H),4.45(dt,J=14.3,7.3 Hz,1H,=CH),2.98(t,J=7.2 Hz,2H,-CO-CH2-),2.48(s,3H,Ar-CH,),2.46-2.41（m,2 H,=C H-CH,-).13C NMR（10 0 M H z,CD Cl,）199.36,16 1.7 5(d,J=215.8 Hz),143.94,135.47,135.37,133.06,132.41,131.93,130.85（d,J=2 33.4 H z）,12 9.6 3,128.58,127.99,127.44,116.42（d,J=2 2 6 H z),110.71,38.71,24.70,21.61.HRMS(ESI)m/z calcdfor C2s H23 FNO,S+(M+H)+424.1382,found424.1379.CTs（E)-N-(4-c h l o r o p h e n y l )-4-m e t h y l-N-(5-o x o-5-phenylpent-1-en-1-yl)benzenesulfonamide(3d)White powder,yield 41%,m.p.144-145.7;IR(KBr)（c m):16 8 3.30,1496.0 1,116 8.7 8,1191.17,671.08,588.80.H NMR（40 0 M H z,CD Cl,）7.97-7.83(m,2H,Ar-H),7.52(dd,J=14.5,6.7 Hz,3H,Ar-H),7.43(t,J=7.7 Hz,2H,Ar-H),7.337.14(m,5H,Ar-H),6.97(dd,J=14.1,6.0 Hz,1H,=CH),6.92-6.79(m,2H,Ar-H),4.39(ddt,J=29.9,14.3,7.3 Hz,1H,=CH),2.97-2.84（m,2H,-CO-CH,-),2.42(s,J=2.8 Hz,3H,Ar-CH,),2.41-2.35（m,2 H,=CH-CH-).13 C NMR（10 0MHz,CDCl,）19 9.2 2,144.0 0,136.8 2,134.8 0,133.05，131.45，131.38，12 9.7 8，12 9.6 9，12 9.6 5,129.51，12 8.58，12 7.98，12 7.44，111.14，38.6 524.71,21.59.HRMS(ESI)m/z calcd for C24H2,CINO,S+(M+H)+440.1087,found 440.1078.BrTs（E)-N-(4-b r o m o p h e n y l )4-m e t h y l-N-(5-o x o-5-phenylpent-1-en-1-yl)benzenesulfonamide(3e)White powder,yield 39%,m.p.87.2-88.7,IR(KBr)（c m):16 93,147 7,136 7,117 2,6 95,58 2.HNMR（40 0 M H z,CD Cl,）8.0 2-7.8 3（m,2 H,A r-H),7.54(dd,J=13.8,7.4 Hz,3H,Ar-H,),7.507.36(m,3H,Ar-H),7.27(d,J=8.0 Hz,2H,Ar-H),期49第杨岚催化联烯胺氮的加成反应构建-烯丙基酮化合物7.20(q,J=8.3,7.8 Hz,2H,Ar-H),7.10(t,J=1.9Hz,1H,Ar-H),6.95(d,J=14.0 Hz,1H,=CH),6.86(d,J=8.0 Hz,1H,Ar-H),4.47(dt,J=14.2,7.2 Hz,1H,=CH),2.94(t,J=7.2 Hz,2H,-CO-CH2-),2.43（s,3H,A r-C H 3),2.39 (d d,J=13.1,6.0 Hz,2H,=CH-CH2-）.13 C NM R（10 0 M H z,CDCl,）8 199.2 1,144.12,136.8 1,135.40,133.2 5,133.06,132.04，130.56，12 9.6 8，12 9.42，12 8.8 1,128.59，12 7.98，12 7.46，111.6 7，38.6 4，2 4.6 8,21.61.HRMS(ESI)m/z calcd for C24H2,BrNO,S*(M+H)+484.0577,found 484.0579.NMeTs(E)-4-methyl-N-(5-oxo-5-phenylpent-1-en-1-yl)-N-(o-tolyl)benzenesulfonamide(3f)Yellow oil,yield 47%,IR（K Br）（c m):16 93,1365,1170,967,666,589.H NMR(400 MHz,CDCl,)8 8.01-7.83(m,2H,Ar-H),7.58(d,J=8.1 Hz,2H,Ar-H),7.53(d,J=7.4 Hz,1H,Ar-H),7.43(t,J=7.6 Hz,2H,Ar-H),7.31-7.22(m,4H,Ar-H),7.10-6.97(m,2H,Ar-H,=CH),6.51(d,J=7.9Hz,1H,Ar-H),4.23（d t,J=14.2,7.2 H z,1H,=CH),2.91(t,J=7.3 Hz,2H,-CO-CH2-),2.43(s,3H,Ar-CH,),2.39（q,J=6.7 H z,2 H,=CH-CH,-),2.15(s,3H,Ar-CH,).13C NMR（10 0 M H z,CD Cl,)199.36,143.70,139.23,136.57,135.13,133.00,131.60,129.61，12 9.48，12 9.10，12 8.7 1，12 8.56,127.98,127.43,126.61,109.67,38.90,24.72,21.5917.83.HRMS(ESI)m/z calcd for C2sH2NO,S+(M+H)+420.1628,found 420.1629.MeMeMeTS(E)-N-mesityl-4-methyl-N-(5-oxo-5-phenylpent-1-en-1-yl)benzenesulfonamide(3g)Light yellow powder,yield 54%,m.p.99.3-100.9,I R（K Br）（c m）:16 93,158 6,136 0,116 5,663,595.29.HNMR（40 0 M H z,CD Cl,）7.8 8（d,J=7.7 Hz,2H,Ar-H),7.63(d,J=7.9 Hz,2H,Ar-H),7.55(t,J=7.5 Hz,1H,Ar-H),7.43(t,J=7.6Hz,2H,Ar-H),7.30-7.22（m,2 H,A r-H),6.95(d,J=13.8 Hz,1H,=CH),6.85(s,2H,Ar-H),4.20(dt,J=14.1,7.3 Hz,1H,=CH),2.91(t,J=7.3Hz,2H,-CO-CH,-),2.42(s,3H,Ar-CH,),2.39（t,J=7.2 Hz,2H,=CH-CH,-),2.26（s,3H,A r-CH,),1.81（s,6 H,A r-CH,).13C NM R（10 0 M H z,CD Cl,）199.43,143.59,138.57,137.64，136.91,132.97,131.08,129.83，12 9.7 6，12 9.6 9，12 8.55，12 7.97,127.27,127.24,107.86,39.13,24.75,21.56,21.01,18.18.HRMS(ESI)m/z calcd for Cz,H3oNO,S*(M+H)*448.1946,found 448.1940.NTs（E)-N-(4-f l u o r o b e n z y l )-4-m e t h y l-N-(5-o x o-5-phenylpent-1-en-1-yl)benzenesulfonamide(3h)White powder,yield 42%,m.p.83.7-85.5,IR(KBr)(cm):1693,1550,1167,952,666,585.H NMR（40 0 M H z,CD Cl）8.2 4-8.17（m,2H,Ar-H),8.01(d,J=8.1 Hz,2H,Ar-H),7.91(td,J=7.3,1.5 Hz,1H,Ar-H),7.80(t,J=7.8 Hz,2H,Ar-H),7.64(d,J=8.0 Hz,2H,Ar-H),7.56(dd,J=8.3,5.4 Hz,2H,Ar-H),7.26(t,J=8.7 Hz,2H,Ar-H),7.04(d,J=14.2 Hz,1H,=CH),5.11(dt,J=14.3,7.2 Hz,1H,=CH),4.76(s,2H,Ar-CH,-N-),3.23(t,J=7.0 Hz,2H,-CO-CH2-),2.77(s,3H,Ar-CH,),2.76-2.68（m,2 H,=CH-CH 2-).13C NM R（10 0 M H z,CD Cl,）199.13，16 1.99（d，J=244.08Hz),143.80,136.81,135.79,131.17（d,J=216Hz),129.80,128.74,128.66,128.56,127.90,126.93,126.63,115.31（d,J=2 2 0 H z）,112.17,48.80,38.73,24.82,21.53.HRMS（ESI)m/z c a l c dfor C2s H2s FNO,S+（M +H)+438.1534,f o u n d438.1536.BrTsBr50第50 卷西南民族大自然科学版）(E)-N-(4-bromophenyl)-N-(5-(4-bromophenyl)-5-oxopent-1-en-1-yl)-4-methylbenzenesulfonamide(3i)White powder,yield 48%,m.p.93.7-95,IR(KBr）（c m ):16 93,1494,12 8 1,116 7,7 53,58 7.HNMR（40 0 M H z,C D C l,）8.2 4-8.17（m,2 H,A r-H),8.01(d,J=8.1 Hz,2H,Ar-H),7.91(td,J=7.3,1.5 Hz,1H,Ar-H),7.80(t,J=7.8 Hz,2H,Ar-H),7.64(d,J=8.0 Hz,2H,Ar-H),7.56(dd,J=8.3,5.4 Hz,2H,Ar-H),7.26(t,J=8.7 Hz,2H,Ar-H),7.04(d,J=14.2 Hz,1H,=CH),5.11(dt,J=14.3,7.2 Hz,1H,=CH),4.76(s,2H,Ar-CH,-N-),3.23(t,J=7.0 Hz,2H,-CO-CH2-),2.77(s,3H,Ar-CH,),2.76-2.68（m,2 H,=CH-CH,-).13C NM R（10 0 M H z，CD Cl,）198.16，144.0 8，135.7 2,135.49,135.41，132.7 2，131.8 9,131.7 8，12 9.6 8,129.58,129.52，12 8.2 3，12 7.43，12 3.0 2，110.8 0,38.63,24.61,21.62.HRMS(ESI)m/z calcd for C24H22 Br,NO,S*(M+H)*561.9682,found 561.9684.3结论本文利用金催化实现了联烯胺与烯基叠氮化合物的加成反应,合成了9个-烯丙基酮产物,反应过程是通过金催化活化联烯胺形成金络合的烯丙基正离子,接着被烯基叠氮发生亲核进攻，最后再水解得到目标产物.该反应的创新点在于，首先，以联烯胺作为烯丙基试剂；其次，以烯基叠氮的双键作为亲核试剂合成-烯丙基酮产物,具有一定的创新性及合成价值.参考文献1SUN S G,CHEN R Y,YU D Q.Structures of two new benzofuran deriv-atives from the bark of mulberry tree(Morus macroura Miq.)J.Journal of Asian Natural Products Research,2001,3(4):253-259.2DU J,HE Z D,JIANG R W,et al.Antiviral flavonoids from the rootbark ofMorus alba LJJ.Phytochemistry,2003,62(8):1235-1238.3JDUTTA S,BHATTACHARYA T,WERZ D B,et al.Transition-metal-catalyzed C-H allylation reactionsJJ.Chem,2021,7(3):555-605.4CRAIG ROBERT A,SMITH RUSSELL C,ROIZEN JENNIFER L,etal.Development of a unifiedenantioselective,convergent synthetic ap-proach toward the furanobutenolide-derived polycyclic norcembranoidditerpenes:asymmetric formation of the polycyclic norditerpenoid carbo-cyclic core by 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