一种含α-氰基取代季碳中心的环烯酮化合物的制备方法转让专利
申请号 : CN202010250039.4
文献号 : CN111499542B
文献日 : 2021-06-04
发明人 : 刘文博 , 陆志武 , 胡旭东
申请人 : 武汉大学
摘要 :
权利要求 :
1.一种含α‑氰基取代季碳中心的环烯酮化合物的制备方法,其特征在于,包含如下步骤:(1)在镍络合物和配体催化下,原料I和II在有机溶剂中发生反应,并加入添加剂;(2)反应结束后,加入酸溶液搅拌后处理;(3)浓缩溶剂,分离提纯,生成III所示的α‑氰基取代季碳中心的环烯酮化合物,其反应方程式如下:其中[Ni]指镍络合物;Ligand指配体;solvent指有机溶剂;additive指添加剂;
1 2 3 1 2
其中R 、R、R 是分别独立的取代基;其中R任选自氢、烷基或芳基;R 任选自烷基、烯基
3 4
或芳基;R 任选自芳基或者烯基;其中Z任选自亚甲基或R取代的胺;其中m任取自0、1、或2;
4
其中n任取自0、1、或2;其中R 任选自烷基、芳基、叔丁氧羰基、苄氧羰基、乙酰基、苯甲酰基
3 3 3 3 3
或者磺酰基;其中R[B]表示R取代的硼酸、R取代的硼酸酐、R取代的三氟硼酸盐、或者R 取代的频哪醇硼酸酯;*表示手性中心;
其中镍络合物为双‑(1,5‑环辛二烯)镍、双(环戊二烯)镍、卤化镍、乙酰丙酮酸镍、硫酸镍、硝酸镍、高氯酸镍、醋酸镍、碳酸镍、对甲苯磺酸镍、三氟甲烷磺酸镍、四氟硼酸镍或者这些物质的水合物、有机溶剂合物中的任意一种;所述的配体具有式A‑K所示结构或者其对映异构体,
14 5 6 7 8 9 10式A‑K中Ar为芳基,Y任选自氧或R 取代的氮原子,所述的取代基R 、R 、R 、R 、R 、R 、
11 12 13 14 5 10R 、R 、R 、R 是独立的取代基;其中R、R 任选自氢、氟、烷基、卤代烷基、卤代烷氧基、环烷
6 7 8 9 13
基、杂环基、烷氨基、烷氧基、芳基或杂芳基;R 、R 、R 、R 、R 任选自氢、甲基、乙基、异丙基、
11 12 14
叔丁基、环己基、芳基或芐基;R 、R 、R 任选自甲基、乙基、异丙基、叔丁基、环己基、芳基;
所述催化剂镍络合物中所含金属镍元素与配体的摩尔比为1:0.5~1:5;
所述有机溶剂为苯、甲苯、二甲苯、乙苯、氯苯,三氟甲苯、氯仿、二氯甲烷、乙腈、异丙醇、环己烷、正己烷、二甲基甲酰胺、乙二醇二甲醚、甲基叔丁基醚、四氢呋喃、1,4‑二氧六环以及其中二种或二种以上混合溶剂;
所述添加剂是指三氟磺酸锌、三氟磺酸铁、六氟磷酸胺、水;
所述原料I和II的物质量之比为2:1~1:3;
所述添加剂和原料I的物质量之比为0.2:1~10:1;
所述步骤(2)酸溶液为盐酸、硫酸、磷酸、醋酸或硝酸中的任意一种;
所述步骤(2)后处理加入酸的量和原料I的物质量之比为1:1~100:1;
所述反应的温度为60℃~120℃;
所述反应的时间为1~48小时。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述配体为具有如式A、式B、式C、式F或式I所示结构的配体。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述镍络合物中所含金属镍元素与配体的摩尔比为1:1~1:1.2。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述有机溶剂为四氢呋喃或甲苯。
5.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述反应的添加剂为4当量的水。
6.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述酸溶液为盐酸。
7.根据权利要求1所述的制备方法,其特征在于,步骤(3)所述分离提纯方法为柱层析、薄层层析或重结晶。
8.根据权利要求7所述的制备方法,其特征在于,所述柱层析使用的洗脱液为乙酸乙酯、二氯甲烷、或者石油醚和乙酸乙酯的混合液,其中石油醚和乙酸乙酯的体积比为1:2~
80:1。
9.一种α‑氰基取代季碳中心的环烯胺化合物IV的制备方法,其特征在于,包含如下步骤:(1)与权利要求1‑8任意一项所述的制备方法的步骤(1)相同;(2)将步骤(1)的产物进行分离提纯,获得α‑氰基取代季碳中心的环烯胺化合物IV,具体方程式如下:其中分离提纯方法与权利要求1中的步骤(3)分离方法一致;
1 2 3
其中R、R 、R、Z、m、n和[B]的范围和权利要求1所述的α‑氰基取代季碳中心的环烯酮的制备方法中的范围一致;[Ni],ligand,solvent和additive也与权利要求1所述的α‑氰基取代季碳中心的环烯酮的制备方法中的指代一致。
说明书 :
一种含α‑氰基取代季碳中心的环烯酮化合物的制备方法
技术领域
背景技术
征。在药物和临床候选药物中,越来越多地发现含有氰基基团。特别重要的是,那些包含氰
基的全碳季碳立体中心的生物活性化合物,可防止化合物的α‑碳氧化,导致有毒的氰化物
释放。[a)Y.Wang,Y.Du,N.Huang,Future Med.Chem.2018,10,2713;b)T.Sterling,
J.J.Irwin,J.Chem.Inf.Model.2015,55,2324.c)F.F.Fleming,L.Yao,P.C.Ravikumar,
L.Funk,B.C.Shook,J.Med.Chem.2010,53,7902;d)J.Michel,J.Tirado‑Rives,
W.L.Jorgensen,J.Am.Chem.Soc.2009,131,15403.e)H.Tanii,K.Hashimoto,
Toxicol.Lett.1984,22,267;b)A.E.Ahmed,N.M.Trieff,Prog.Drug Metab.1983,7,229.]。
此外,氰基基团是有机合成中最有用的官能团之一,可以轻松转化为多种官能团,例如羧
酸,醛,胺,恶唑啉和哌啶等[a)F.F.Fleming,Nat.Prod.Rep.1999,16,597;b)K.Friedrich,
K.Wallenfels,The Chemistry of the Cyano Group;Wiley‑Interscience:New
York.1970;c)Z.Zhang,X.Zhang,D.A.Nagib,Chem 2019,5,3127.]。因此在合成化学领域中
受到科学家们的广泛关注。目前已经报道的合成这类含氰基手性季碳中心结构的方法主要
包括:(1)α‑氰基羰基亲电官能化[a)R .Kuwano ,H.Miyazaki ,Y.Ito,
J.Organomet.Chem.2000,603,18;b)Y.Kawato,N.Takahashi,N.Kumagai,M.Shibasaki,
Org.Lett.2010,12,1484;c)S.Mukhopadhyay,U.Nath,S.C.Pan,Adv.Synth.Catal.2017,
359,3911;d)K.Nakashima,Y.Noda,S.‑i.Hirashima,Y.Koseki,T.Miura,
J.Org.Chem.2018,83,2402;e)K.Nagata,D.Sano,Y.Shimizu,M.Miyazaki,T.Kanemitsu,
T.Itoh,Tetrahedron:Asymmetry 2009,20,2530;f)For a decarboxylative alkylation:
L.Yin,M.Kanai,M.Shibasaki,J.Am.Chem.Soc.2009,131,9610.]。(b)乙烯酮亚胺亲电官能
化[a)A.H.Mermerian,G.C.Fu,Angew.Chem.Int.Ed.2005,44,949;b)S.E.Denmark,
T.W.Wilson,M.T.Burk,J.R.Heemstra,Jr.J.Am.Chem.Soc.2007,129,14864;c)J.Zhao,
X.Liu,W.Luo,M.Xie,L.Lin,X.Feng,Angew.Chem.Int.Ed.2013,52,3473;d)J.Zhao,
B.Fang,W.Luo,X.Hao,X.Liu,L.Lin,X.Feng,Angew.Chem.Int.Ed.2015,54,241;e)
B.W.H.Turnbull,P.A.Evans,J.Am.Chem.Soc.2015,137,6156;f)Z.Jiao,K.W.Chee,
J.Zhou,J.Am.Chem.Soc.2016,138,16240;g)For a seminal report:A.Q.Mi,Z.Y.Wang,
Y.Z.Jiang,Tetrahedron:Asymmetry,1993,4,1957]。(c)3‑二羰基α‑氰化[a)R.Chowdhury,
J. J.Novacek,M.Waser,Tetrahedron Lett.2015,56,1911;b)M.Chen,Z.‑
T.Huang,Q.‑Y.Zheng,Org Biomol.Chem.2015,13,8812;c)J.‑S.Qiu,Y.‑F.Wang,G.‑R.Qi,
P.G.Karmaker,H.‑Q.Yin,F.‑X.Chen,Chem.Eur.J.2017,23,1775.]。
[S.F.Rach,F.E.Kühn,Chem.Rev.2009,109,2061]和氰基的微小空间尺寸[E.L.Eliel,
S.H.Wilen,L.N.Mander,Stereochemistry of Organic Compounds,Wiley:New York,
1994,pp 696.],以及在过渡金属催化和有机金属试剂存在下,丙二腈会脱氰分解[a)
L.R.Mills,J.M.Graham,P.Patel,S.A.L.Rousseaux,J.Am.Chem.Soc.2019,141,19257;b)
J.T.Reeves,C.A.Malapit,F.G.Buono,K.P.Sidhu,M.A.Marsini,C.A.Sader,
K.R.Fandrick,C.A.Busacca,C.H.Senanayake,J.Am.Chem.Soc.2015,137,9481;c)
S.Alazet,M.S.West,P.Patel,S.A.L.Rousseaux,Angew.Chem.Int.Ed.2019,58,10300]。
33%ee的手性控制[K.Tanaka,N.Suzuki,G.Nishida,Eur.J.Org.Chem.2006,2006,3917;]。
2010年,Ikariya基团报导了钌催化的水解反应,得到了54%的收率和30%ee的手性控制。
[S.Kamezaki,S.Akiyama,Y.Kayaki,S.Kuwata,T.Ikariya,Tetrahedron:Asymmetry 2010,
21,1169]。但是,在这两种情况下,不仅对映选择性差,而且为单一底物,并且产物结构单
一。
发明内容
剂;(2)反应结束后,加入酸溶液搅拌后处理;(3)浓缩溶剂,分离提纯,生成III所示的α‑氰
基取代季碳中心的环烯酮化合物;其反应方程式如下:
烯基或芳基;R任选自芳基或者烯基;其中Z任选自亚甲基或R取代的胺;其中m任取自0、1、
4
或2;其中n任取自0、1、或2;其中R 任选自烷基、芳基、叔丁氧羰基、苄氧羰基、乙酰基、苯甲
酰基或者磺酰基;其中[B]表示硼酸、硼酸酐、三氟硼酸盐、或者频那醇硼酸酯;*表示手性中
心;
者这些物质的水合物、有机溶剂合物中的任意一种;
或R 取代的氮原子,所述的取代基R、R、R、R、R、R 、R 、R 、R 、R 是独立的取代基;其中
5 10
R、R 任选自氢、氟、烷基、卤代烷基、卤代烷氧基、环烷基、杂环基、烷氨基、烷氧基、芳基或
6 7 8 9 13 11
杂芳基;R 、R 、R 、R 、R 任选自氢、甲基、乙基、异丙基、叔丁基、环己基、芳基或芐基;R 、
12 14
R 、R 任选自甲基、乙基、异丙基、叔丁基、环己基、芳基;
丁基醚、四氢呋喃、1,4‑二氧六环以及其中二种或二种以上混合溶剂;
代季碳中心的环烯酮制备方法中的步骤(2)酸后处理,直接将步骤(1)的产物进行分离提
纯,获得α‑氰基取代季碳中心的环烯胺化合物IV,具体方程式如下:
的制备方法中的指代一致。
具体实施方式
制的对映选择性,由高效液相测定。
腈基取代环烯酮化合物的手性控制,由高效液相测定。
腈基取代环烯酮化合物的手性控制,由高效液相测定。
示添加剂;ee指α‑腈基取代环烯酮化合物的手性控制,由高效液相测定;[a]表示使用了
2equiv的水;[b]表示使用了10equiv的水。
液相测定。
的1mL甲苯溶液中,室温下搅拌30分钟。接着加入反应物I(0.2mmol)和反应物II
(0.4mmol,),最后再补加1mL甲苯和H2O(15μL,0.8mmol)。80℃油浴条件下反应,至TLC监测
原料反应完全(约24h)。体系恢复至室温,加入1M盐酸水溶液(1.0mL)进行后处理,并搅拌30
分钟.混合体系用乙酸乙酯(10mL x 3)萃取,有机相饱和水萃取,无水硫酸钠干燥,过滤。旋
转蒸发除去溶剂,选用200‑300目的硅胶和石油醚与乙酸乙酯的混合溶剂作为洗脱液进行
柱层析分离,得到目标产物III,产物的ee由配备手性分离柱的高相液相色谱测定。
terphenyl]‑4'‑carbonitrile],其结构式如下:
13
1H),2.39(dt,J=13.7,4.6Hz,1H),2.24–2.17(m,1H). C NMR(100MHz,CDCl3)δ190.2,
158.5,139.5,135.8,134.8,134.5,130.9,130.7,128.8,128.7,128.24,128.20,127.9,
+ +
127.8,127.5,118.7,47.7,39.7,30.2,29.8.HRMS(ESI)m/z calc’d for C26H21NONa[M+Na] :
386.1515,found 386.1518.
1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
2.1,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.38–7.35(m,5H),7.22–7.18
(m,3H),6.99–6.92(m,6H),3.53(AB,J=14.0Hz,1H),3.12–3.04(m,2H),2.92(dt,J=19.5,
13
4.6Hz,1H),2.38(dt,J=13.7,4.6Hz,1H),2.26(s,3H),2.23–2.16(m,1H). C NMR(100MHz,
CDCl3)δ190.2,158.5,138.9,136.5,135.4,135.1,134.6,130.9,130.6,128.9,128.7,
+
128.3,128.0,127.8,127.4,118.8,47.6,39.7,30.1,29.7,21.4.HRMS(ESI)m/z calc’d
+
for C27H23NONa[M+Na]:400.1672,found 400.1674.
1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.2,CHCl3).Rf=0.2(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.31(m,5H),7.24–7.17
(m,3H),7.00–6.96(m,4H),6.68(d,J=8.8Hz,2H),3.74(s,3H),3.53(AB,J=14.0Hz,1H),
3.10(BA,J=13.9Hz,1H),3.05(dd,J=9.9,4.9Hz,1H),2.93(dt,J=19.5,4.6Hz,1H),2.37
13
(dt,J=13.7,4.6Hz,1H),2.23–2.14(m,1H). C NMR(100MHz,CDCl3)δ190.1,159.9,158.0,
135.4,135.0,134.6,131.5,131.0,130.6,130.1,128.7,128.1,127.7,127.4,118.9,
+ +
113.6,55.3,47.6,39.7,30.0,29.5.HRMS(ESI)m/z calc’d for C27H23O2Na[M+Na] :
416.1621,found 416.1627.
1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.5,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.30(m,5H),7.22–7.19
(m,3H),7.05–6.99(m,2H),6.96–6.92(m,2H),6.89–6.83(m,2H),3.53(d,J=14.0Hz,1H),
3.12–3.04(m,2H),2.89(dt,J=19.6,4.5Hz,1H),2.38(dt,J=13.7,4.5Hz,1H),2.23–2.16
13
(m,1H). C NMR(100MHz,CDCl3)δ190.1,162.6(d,J=249.9Hz),157.1,136.0,135.5(d,J=
3.1Hz),134.7,134.5,130.9,130.7,130.3(d,J=8.1Hz),128.8,128.1,127.7(d,J=
19
18.4Hz),118.6,115.5,115.3,47.6,39.6,30.1,29.7. F NMR(376MHz,CDCl3)δ–
+ +
111.69.HRMS(ESI)m/z calc’d for C26H20NOFNa[M+Na]:404.1421,found 404.1423.
1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.5,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.31(m,5H),7.23–7.20
(m,3H),7.15(d,J=8.3Hz,2H),7.00–6.92(m,4H),3.53(d,J=13.9Hz,1H),3.12–3.03(m,
13
2H),2.88(dt,J=19.5,4.4Hz,1H),2.39(dt,J=13.8,4.4Hz,1H),2.23–2.16(m,1H). C
NMR(100MHz,CDCl3)δ190.1,156.8,137.9,136.1,134.7,134.5,134.4,130.8,130.7,
+
129.7,128.8,128.6,128.2,127.8,127.7,118.6,47.6,39.6,30.1,29.6.HRMS(ESI)m/z
+
calc’d for C26H20NOClNa[M+Na]:420.1126,found 420.1126.
1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
0.9,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.39–7.29(m,7H),7.23–7.19
(m,3H),6.96–6.89(m,4H),3.52(d,J=14.0Hz,1H),3.11–3.03(m,2H),2.87(dt,J=19.6,
13
4.5Hz,1H),2.38(dt,J=13.8,4.5Hz,1H),2.23–2.15(m,1H). C NMR(100MHz,CDCl3)δ
190.1,156.8,138.4,136.1,134.5,134.4,131.5,130.8,130.7,129.9,128.8,128.2,
+
127.9,127.8,123.0,118.6,47.6,39.6,30.1,29.6.HRMS(ESI )m/z calc’d for
+
C26H20NOBrNa[M+Na]:464.0620,found 464.0624.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
2.1,CHCl3).Rf=0.2(PE:EA=15:1).H NMR(400MHz,CDCl3)7.44(d,J=8.1Hz,2H),7.40–
7.32(m,5H),7.22–7.18(m,3H),7.15(d,J=8.1Hz,2H),6.95–6.90(m,2H),3.54(d,J=
14.0Hz,1H),3.15–3.06(m,2H),2.88(dt,J=19.6,4.4Hz,1H),2.41(dt,J=13.8,4.5Hz,
13
1H),2.26–2.19(m,1H). C NMR(100MHz,CDCl3)δ190.1,156.4,143.2,136.7,134.3,134.1,
130.7,130.6,130.4(q,J=32.7Hz),128.8,128.5,128.2,127.91,127.87,125.3(q,J=
19
3.8Hz),123.8(q,J=272.3Hz),118.5,47.6,39.6,30.2,29.6. F NMR(376MHz,CDCl3)δ–
+ +
62.82.HRMS(ESI)m/z calc’d for C27H20F3NONa[M+Na]:454.1389,found 454.1390.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
2.1,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.32(m,5H),7.22–7.20
(m,3H),7.07(d,J=8.6Hz,2H),7.02(d,J=8.5Hz,2H),6.95–6.93(m,2H),3.54(d,J=
14.0Hz,1H),3.13–3.05(m,2H),2.90(dt,J=19.6,4.5Hz,1H),2.40(dt,J=13.8,4.5Hz,
13
1H),2.25–2.18(m,1H). C NMR(100MHz,CDCl3)δ190.1,156.6,149.1,138.0,136.3,134.4,
130.8,130.6,129.9,128.8,128.1,127.8,127.7,120.5,120.4(q,J=256.3Hz),118.6,
19 +
47.6,39.6,30.1,29.6. F NMR(376MHz,CDCl3)δ–57.78.HRMS(ESI)m/z calc’d for
+
C27H20NO2F3Na[M+Na]:470.1338,found 470.1329.
terphenyl]‑4,4'‑dicarbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.2(PE:EA=5:1).H NMR(400MHz,CDCl3)δ7.48–7.45(m,2H),7.40–7.31
(m,5H),7.24–7.17(m,3H),7.16–7.12(m,2H),6.93–6.89(m,2H),3.53(AB,J=14.0Hz,1H),
13
3.14–3.05(m,2H),2.86(dt,J=19.6,4.4Hz,1H),2.44–2.38(m,1H),2.25–2.18(m,1H). C
NMR(100MHz,CDCl3)δ189.9,155.7,144.2,137.0,134.2,133.8,132.1,130.7,130.6,
+
128.9,128.8,128.3,128.1,127.9,118.3,112.3,47.6,39.5,30.2,29.4.HRMS(ESI)m/z
+
calc’d for C27H20N2ONa[M+Na]:411.1468,found 411.1457.
[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.6,CHCl3).Rf=0.2(PE:EA=5:1).H NMR(400MHz,CDCl3)δ9.91(s,1H),7.69(d,J=
8.3Hz,,2H),7.41–7.32(m,5H),7.21–7.15(m,5H),6.96–6.91(m,2H),3.54(AB,J=14.0Hz,
1H),3.16–3.07(m,2H),2.90(dt,J=19.6,4.5Hz,1H),2.42(dt,J=13.8,4.5Hz,1H),2.27–
13
2.20(m,1H). C NMR(100MHz,CDCl3)δ191.6,190.0,156.6,145.7,136.8,135.9,134.3,
134.1,130.8,130.7,129.6,128.8,128.2,128.0,127.9,118.5,47.6,39.6,30.3,
+ +
29.6.HRMS(ESI)m/z calc’d for C27H21NO2Na[M+Na]:414.1465,found 414.1468.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4‑carboxylate],其结构式如下:
1.0,CHCl3).Rf=0.2(PE:EA=5:1).H NMR(400MHz,CDCl3)δ7.84(d,J=8.1Hz,2H),7.40–
7.31(m,5H),7.20–7.17(m,3H),7.11(d,J=8.1Hz,2H),6.95–6.91(m,2H),3.87(s,3H),
3.53(d,J=14.0Hz,1H),3.14–3.06(m,2H),2.90(dt,J=19.6,4.5Hz,1H),2.41(dt,J=
13
13.8,4.5Hz,1H),2.26–2.19(m,1H). C NMR(100MHz,CDCl3)δ190.0,166.5,157.1,144.1,
136.4,134.3,134.2,130.7,130.6,130.0,129.5,128.8,128.2,128.1,127.83,127.79,
+ +
118.5,52.3,47.6,39.5,30.2,29.5.HRMS(ESI )m/z calc’d for C28H23NO3Na[M+Na] :
444.1570,found 444.1558.
5',6'‑tetrahydro‑[1,1':2',1”‑terphenyl]‑4‑carboxamide],其结构式如下:
1.7,CHCl3).Rf=0.2(PE:EA=1:1).H NMR(400MHz,CDCl3)δ7.39–7.29(m,5H),7.22(d,J=
8.0Hz,2H),7.18–7.14(m,3H),7.06(d,J=8.0Hz,2H),6.95–6.91(m,2H),3.52(AB,J=
13
13.9Hz,1H),3.12–2.87(m,9H),2.39(dt,J=13.7,4.5Hz,1H),2.24–2.17(m,1H). C NMR
(100MHz,CDCl3)δ190.1,170.8,157.3,140.8,136.2,136.1,134.5,134.4,130.8,130.6,
128.7,128.2,128.0,127.8,127.7,127.1,118.6,47.6,39.6,30.1,35.4(br),29.6.HRMS
+ +
(ESI)m/z calc’d for C29H26N2O2Na[M+Na]:457.1886,found 457.1892.
tetrahydro‑[1,1':2',1”‑terphenyl]‑3‑carboxylate],其结构式如下:
1.6,CHCl3).Rf=0.2(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.87–7.83(m,2H),7.41–7.31
(m,5H),7.21–7.16(m,4H),7.12(dt,J=7.8,1.6Hz,1H),6.97–6.92(m,2H),3.88(s,3H),
3.53(AB,J=14.0Hz,1H),3.15–3.06(m,2H),2.95(dt,J=19.7,4.6Hz,1H),2.41(dt,J=
13
13.7,4.6Hz,1H),2.26–2.19(m,1H). C NMR(100MHz,CDCl3)δ190.1,166.5,157.1,139.8,
136.4,134.4,134.3,132.9,130.8,130.6,130.3,129.7,129.0,128.8,128.4,128.1,
+
127.8,127.7,118.6,52.4,47.6,39.6,30.1,29.6.HRMS(ESI)m/z calc’d for C28H23NO3Na
+
[M+Na]:444.1570,found 444.1578.
1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
0.6,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.42–7.30(m,5H),7.22–7.19
(m,5H),7.02–6.94(m,4H),6.61(dd,J=17.6,10.9Hz,1H),5.71(d,J=17.6Hz,1H),5.25
(d,J=10.9Hz,1H),3.54(AB,J=14.0Hz,1H),3.13–3.05(m,2H),2.92(dt,J=19.5,4.4Hz,
13
1H),2.39(dt,J=13.7,4.5Hz,1H),2.24–2.17(m,1H). C NMR(100MHz,CDCl3)δ190.2,
157.9,138.8,137.9,136.1,135.6,134.9,134.5,130.9,130.6,128.8,128.6,128.0,
+
127.8,127.5,126.0,118.7,115.2,47.7,39.7,30.2,29.5.HRMS(ESI)m/z calc’d for
+
C28H24NO[M+H]:390.1852,found 390.1846.
3‑carbonitrile,其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.44–7.29(m,8H),7.19–7.16
(m,2H),7.12–7.08(m,2H),5.66–5.65(m,1H),3.51(AB,J=14.0Hz,1H),3.10–3.02(m,2H),
13
2.92(dt,J=18.8,4.7Hz,1H),2.36(dt,J=13.7,4.7Hz,1H),2.19–2.12(m,1H). C NMR
(100MHz,CDCl3)δ189.8,147.7,144.5,143.2,136.1,134.6,134.0,130.6,129.9,128.9,
+
128.7,128.3,127.7,124.7,118.8,110.0,47.5,39.6,29.8,27.0.HRMS(ESI)m/z calc’d
+
for C24H19NO2Na[M+Na]:376.1308,found 376.1309.
biphenyl]‑3‑carbonitrile],其结构式如下:
1.5,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.39–7.31(m,8H),7.13–7.03
(m,4H),6.56(dd,J=5.2,1.3Hz,1H),3.52(AB,J=14.0Hz,1H),3.18–2.98(m,3H),2.38
13
(dt,J=13.7,4.6Hz,1H),2.21–2.14(m,1H). C NMR(100MHz,CDCl3)δ190.3,150.9,139.7,
135.9,134.6,130.6,130.4,128.8,128.6,128.1,128.0,127.8,127.7,125.2,118.8,47.5,
+ +
39.7,29.9,28.7.HRMS(ESI)m/z calc’d for C24H19NOSNa[M+Na] :392.1080,found
392.1083.
2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.31(m,5H),7.21–7.16
(m,3H),7.07–7.04(m,2H),6.99(AB,J=7.8Hz,2H),6.84(BA,J=7.7Hz,2H),3.53(AB,J=
13.9Hz,1H),3.13–3.04(m,2H),2.92(dt,J=19.6,4.6Hz,1H),2.38(dt,J=13.7,4.6Hz,
13
1H),2.27(s,3H),2.23–2.16(m,1H). C NMR(100MHz,CDCl3)δ190.4,158.0,139.7,137.2,
135.6,134.6,131.7,130.7,130.6,128.74,128.71,128.6,128.23,128.22,127.8,118.8,
+ +
47.6,39.6,30.1,29.8,21.4.HRMS(ESI)m/z calc’d for C27H23NONa[M+Na] :400.1672,
found 400.1677.
[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.3,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.31(m,5H),7.20–7.18
(m,3H),7.07–7.03(m,2H),6.86(d,J=8.7Hz,2H),6.72(d,J=8.6Hz,2H),3.75(s,3H),
3.53(d,J=14.0Hz,1H),3.13–3.03(m,2H),2.91(dt,J=19.6,4.6Hz,1H),2.38(dt,J=
13
13.7,4.6Hz,1H),2.19(ddd,J=14.1,9.6,5.0Hz,1H). C NMR(100MHz,CDCl3)δ190.6,
158.8,157.9,139.8,135.3,134.6,132.2,130.7,128.8,128.6,128.3,128.2,127.8,
+
127.0,118.8,113.5,55.3,47.7,39.7,30.2,29.8.HRMS(ESI)m/z calc’d for C27H23NO2Na
+
[M+Na]:416.1621,found 416.1618.
2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.40–7.30(m,7H),7.24–7.18
(m,3H),7.03–7.01(m,2H),6.82(d,J=8.5Hz,2H),3.52(d,J=14.0Hz,1H),3.13–3.05(m,
2H),2.92(dt,J=19.7,4.5Hz,1H),2.39(dt,J=13.8,4.6Hz,1H),2.20(ddd,J=14.2,9.7,
13
4.8Hz,1H). C NMR(100MHz,CDCl3)δ190.0,159.2,139.2,134.6,134.4,133.7,132.6,
131.2,130.6,129.0,128.8,128.5,128.1,127.9,121.8,118.6,47.6,39.6,30.1,
+ +
29.8.HRMS(ESI)m/z calc’d for C26H20BrNONa[M+Na]:464.0620,found 464.0623.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.45(d,J=8.1Hz,2H),7.41–
7.33(m,5H),7.25–7.18(m,3H),7.08(d,J=8.0Hz,2H),7.04–7.00(m,2H),3.54(AB,J=
14.0Hz,1H),3.17–3.09(m,2H),2.95(dt,J=19.7,4.5Hz,1H),2.42(dt,J=13.8,4.6Hz,
13
1H),2.27–2.19(m,1H). C NMR(100MHz,CDCl3)δ189.9,159.9,138.9,138.7,134.6,134.3,
131.4,130.6,129.5(q,J=32.7Hz),129.2,128.8,128.5,128.1,127.9,124.9(q,J=
19
3.7Hz),124.2(q,J=272.5Hz),118.5,47.6,39.6,30.1,29.9. F NMR(376MHz,CDCl3)δ–
+ +
62.59.HRMS(ESI)m/z calc’d for C27H20NOF3Na[M+Na]:454.1389,found 454.1391.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4‑carboxylate],其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.86(d,J=8.3Hz,2H),7.40–
7.31(m,5H),7.23–7.13(m,3H),7.04–6.99(m,4H),3.87(s,3H),3.53(d,J=13.9Hz,1H),
3.16–3.07(m,2H),2.94(dt,J=19.7,4.5Hz,1H),2.40(dt,J=13.8,4.6Hz,1H),2.25–2.18
13
(m,1H). C NMR(100MHz,CDCl3)δ189.8,166.9,159.6,139.9,139.0,135.0,134.4,131.1,
130.6,129.2,129.1,129.0,128.8,128.4,128.1,127.9,118.5,52.2,47.6,39.6,30.1,
+ +
29.9.HRMS(ESI)m/z calc’d for C28H23NO3Na[M+Na]:444.1570,found 444.1571.
biphenyl]‑4‑carbonitrile],其结构式如下:
0.85,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.76–7.73(m,1H),7.68–
7.64(m,2H),7.47–7.46(m,1H),7.45–7.32(m,7H),7.15–7.03(m,6H),3.57(AB,J=14.0Hz,
1H),3.19–3.11(m,2H),2.98(dt,J=19.7,4.6Hz,1H),2.43(dt,J=13.7,4.6Hz,1H),2.28–
13
2.13(m,1H). C NMR(100MHz,CDCl3)δ190.4,158.8,139.5,135.6,134.6,133.1,132.6,
132.4,130.7,130.4,128.8,128.7,128.6,128.4,128.3,128.2,127.8,127.7,127.4,
+ +
126.2,126.0,118.8,47.8,39.7,30.2,29.9.HRMS(ESI)m/z calc’d for C30H23NONa[M+Na] :
436.1672,found 436.1675.
biphenyl]‑4‑carbonitrile],其结构式如下:
1.4,CHCl3).Rf=0.4(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.41–7.32(m,5H),7.30–7.26
(m,3H),7.24(dd,J=5.1,1.2Hz,1H),7.18–7.13(m,2H),6.84(dd,J=5.1,3.6Hz,1H),6.68
(dd,J=3.6,1.2Hz,1H),3.56(AB,J=14.0Hz,1H),3.13–3.05(m,2H),2.94(dt,J=20.0,
13
4.7Hz,1H),2.39(dt,J=13.8,4.7Hz,1H),2.24–2.17(m,1H). C NMR(100MHz,CDCl3)δ
189.6,159.6,139.9,134.8,134.4,130.6,130.1,129.1,128.9,128.8,128.6,127.9,
+
127.8,127.1,126.3,118.6,47.9,39.8,30.4,30.0.HRMS(ESI )m/z calc’d for
+
C24H19NOSNa[M+Na]:392.1080,found 392.1081.
tetrahydro‑[1,1'‑biphenyl]‑4‑carbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.4(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.41–7.30(m,8H),7.28–7.26
(m,2H),5.64(s,1H),3.49(d,J=14.0Hz,1H),3.05–2.94(m,2H),2.82(dtd,J=19.6,4.6,
1.6Hz,1H),2.30(dt,J=13.7,4.6Hz,1H),2.11–2.04(m,1H),1.66(d,J=1.5Hz,3H),1.21
(d,J=1.3Hz,3H).
128.7,128.2,127.9,127.7,118.8,118.2,47.6,39.6,30.3,29.2,25.5,20.1.HRMS(ESI)
+
m/z calc’d for C24H23NONa[M+Na]:364.1672,found 364.1679.
carbonitrile],其结构式如下:
0.4,CHCl3).Rf=0.3(PE:EA=15:1).H NMR(400MHz,CDCl3)δ7.44–7.28(m,8H),7.23–7.19
(m,2H),3.48(AB,J=13.9Hz,1H),3.03(BA,J=13.9Hz,1H),2.94–2.85(m,1H),2.74–2.65
(m,1H),2.28(dt,J=13.6,4.8Hz,1H),2.07(ddd,J=13.9,9.3,4.8Hz,1H),1.80(t,J=
13
1.9Hz,3H). C NMR(100MHz,CDCl3)δ191.4,157.3,140.1,134.6,130.6,130.3,128.8,
+
128.7,128.6,127.8,127.1,119.0,47.4,39.8,30.4,29.7,13.9.HRMS(ESI)m/z calc’d
+
for C21H19NONa[M+Na]:324.1359,found 324.1359.
2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
0.5,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.50(d,J=8.3Hz,2H),7.23
(d,J=8.4Hz,2H),7.20–7.15(m,6H),7.06–7.02(m,2H),6.97–6.92(m,2H),3.48(d,J=
14.0Hz,1H),3.16–3.06(m,2H),2.93(dt,J=19.7,4.4Hz,1H),2.37(dt,J=13.6,4.4Hz,
13
1H),2.19(ddd,J=14.1,10.1,4.8Hz,1H). C NMR(100MHz,CDCl3)δ189.9,158.6,139.4,
135.7,134.7,133.5,132.3,131.9,130.9,128.7,128.3,128.2,128.0,127.5,122.0,
118.4,47.4,39.1,30.2,29.8.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.2,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ8.15(d,J=8.2Hz,1H),7.91
(dd,J=8.0,1.6Hz,1H),7.86(d,J=8.2Hz,1H),7.62(d,J=7.0Hz,1H),7.60–7.48(m,3H),
7.23–7.14(m,6H),7.05–6.95(m,4H),4.09(AB,J=14.8Hz,1H),3.64(BA,J=14.7Hz,1H)AB
BA,3.06(dt,J=19.7,7.7Hz,1H),2.85(dt,J=19.7,4.1Hz,1H),2.29(dd,J=7.7,4.1Hz,
13
2H). C NMR(100MHz,CDCl3)δ190.4,158.7,139.5,135.8,134.9,134.1,132.9,131.1,
130.9,129.3,129.1,128.7,128.5,128.21,128.19,127.9,127.5,126.4,125.9,125.6,
+ +
124.0,118.7,48.1,34.8,30.9,30.0.HRMS(ESI)m/z calc’d for C30H23NONa[M+Na] :
436.1672,found 436.1674.
1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.42(s,1H),7.19–7.15(m,
6H),7.06–7.04(m,2H),6.96–6.94(m,2H),6.39–6.35(m,2H),3.53(AB,J=15.2Hz,1H),
3.27(BA,J=15.2Hz,1H),3.15(ddd,J=19.7,9.7,4.8Hz,1H),2.97(dt,J=19.7,4.7Hz,
13
1H),2.53(dt,J=13.9,4.6Hz,1H),2.26(ddd,J=14.2,9.7,4.8Hz,1H). C NMR(100MHz,
CDCl3)δ189.7,158.7,149.1,142.6,139.5,135.6,134.7,130.9,128.7,128.2,128.1,
+
127.9,127.5,118.5,110.9,109.8,47.2,32.5,30.5,29.7.HRMS(ESI)m/z calc’d for
+
C24H20NO2[M+H]:354.1489,found 354.1482.
tetrahydro‑[1,1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
110.47(c 0.6,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.19–7.15(m,6H),
7.05–7.03(m,2H),6.94–6.92(m,2H),5.30(t,J=7.5Hz,1H),3.13(ddd,J=19.6,8.9,
4.9Hz,1H),2.96–2.88(m,2H),2.59–2.53(m,2H),2.29(ddd,J=13.8,9.0,4.9Hz,1H),1.80
13
(s,3H),1.72(s,3H). C NMR(100MHz,CDCl3)δ190.7,158.0,139.6,137.9,135.7,134.8,
130.9,128.6,128.23,128.19,127.9,127.4,119.2,116.9,47.2,32.5,30.4,29.7,26.2,
+ +
18.4.HRMS(ESI)m/z calc’d for C24H23NONa[M+Na]:364.1672,found 364.1678;
terphenyl]‑4'‑carbonitrile],其结构式如下:
(c 1.0,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.20–7.15(m,6H),7.07–
7.03(m,2H),6.96–6.91(m,2H),5.99–5.89(m,1H),5.33–5.28(m,2H),3.15(ddd,J=19.7,
9.1,5.0Hz,1H),2.98–2.91(m,2H),2.62–2.53(m,2H),2.29(ddd,J=13.9,9.1,4.9Hz,1H)
13
. C NMR(100MHz,CDCl3)δ190.3,158.2,139.6,135.7,134.8,131.4,130.9,128.7,128.3,
+
128.2,127.9,127.5,121.1,118.7,46.6,38.3,30.5,29.7.HRMS(ESI)m/z calc’d for
+
C22H19NONa[M+Na]:336.1359,found 336.1363.
1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
60.65(c 0.4,CHCl3).Rf=0.2(PE:EA=5:1).H NMR(400MHz,CDCl3)δ7.20–7.14(m,6H),
7.06–7.02(m,2H),6.94–6.90(m,2H),3.11(ddd,J=19.7,7.5,5.2Hz,1H),3.03–2.96(m,
1H),2.96–2.88(m,1H),2.79(ddd,J=18.3,9.5,5.4Hz,1H),2.61(ddd,J=13.8,6.4,
5.1Hz,1H),2.45(ddd,J=14.4,9.6,5.7Hz,1H),2.35(ddd,J=13.7,7.5,5.0Hz,1H),2.21
13
(s,3H),2.12(ddd,J=14.4,9.7,5.5Hz,1H). C NMR(100MHz,CDCl3)δ206.9,190.9,157.9,
139.4,135.5,134.6,130.9,128.7,128.3,128.2,127.9,127.5,118.9,46.7,39.4,32.0,
+ +
30.2,29.4,27.8.HRMS(ESI )m/z calc’d for C23H21NO2Na[M+Na] :366.1465,found
366.1469.
1':2',1”‑terphenyl]‑4'‑carbonitrile],其结构式如下:
1.6,CHCl3).Rf=0.4(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.20–7.13(m,6H),7.06–7.01
(m,2H),6.94–6.91(m,2H),3.11(ddd,J=19.6,7.6,5.0Hz,1H),2.93(ddd,J=19.6,6.4,
4.9Hz,1H),2.63(ddd,J=13.7,6.4,5.0Hz,1H),2.36(ddd,J=13.7,7.6,4.9Hz,1H),2.08
(dd,J=14.4,6.5Hz,1H),1.99–1.90(m,1H),1.87–1.81(m,1H),1.80–1.58(m,5H),1.37–
13
1.25(m,2H),1.19(tt,J=12.5,3.1Hz,1H),1.15–1.04(m,2H). C NMR(100MHz,CDCl3)δ
191.4,157.3,139.6,135.4,134.9,130.9,128.6,128.22,128.19,127.9,127.4,119.8,
+
46.5,40.6,34.8,34.1,31.3,29.4,26.3,26.23,26.16.HRMS(ESI )m/z calc’d for
+
C26H27NONa[M+Na]:392.1985,found 392.1992.
4'‑carbonitrile],其结构式如下:
(c 0.9,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.20–7.15(m,6H),7.07–
7.04(m,2H),6.95‑6.92(m,2H),3.21(ddd,J=19.6,9.8,4.9Hz,1H),2.95(dt,J=19.6,
4.5Hz,1H),2.57(dt,J=13.7,4.6Hz,1H),2.30(ddd,J=14.2,9.8,4.8Hz,1H),1.67(s,
13
3H). C NMR(100MHz,CDCl3)δ190.9,158.2,139.6,135.4,134.8,130.9,128.6,128.24,
128.21,127.9,127.4,119.8,42.3,33.6,29.9,21.3.
4'‑carbonitrile],其结构式如下:
1.4,CHCl3).Rf=0.3(PE:EA=5:1).H NMR(400MHz,CDCl3)δ7.51–7.36(m,5H),7.22–7.13
13
(m,6H),7.04–6.96(m,4H),3.14–3.02(m,1H),2.98–2.81(m,3H). C NMR(100MHz,CDCl3)δ
189.8,158.3,139.5,136.3,134.6,134.4,131.0,129.3,129.0,128.7,128.2,128.1,
+
127.9,127.5,127.1,119.1,52.5,33.9,29.6.HRMS(ESI)m/z calc’d for C25H19NONa[M+
+
Na]:372.1359,found 372.1363.
1.2,CHCl3).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.39–7.26(m,11H),7.17–
13
7.14(m,2H),7.13–7.10(m,2H),3.46–3.40(m,2H),3.32–3.27(m,2H). C NMR(100MHz,
CDCl3)δ198.7,166.2,137.4,134.0,133.8,130.9,130.8,130.2,129.4,128.9,128.8,
+
128.7,128.1,128.1,119.9,46.7,42.1,39.8.HRMS(ESI)m/z calc’d for C25H19NONa[M+
+
Na]:372.1359,found 372.1361.
下:
=13.9Hz,1H),3.07–2.98(m,2H),2.91(dt,J=18.9,5.0,1H),2.35(dt,J=13.8,5.0Hz,
13
1H),2.10(ddd,J=13.8,8.9,4.8Hz,1H). C NMR(100MHz,CDCl3)δ190.6,160.4,137.3,
134.4,131.1,130.5,129.2,128.8,127.8,126.4,122.7,118.7,47.4,39.2,30.7,25.4.
1.0,CHCl3).Rf=0.4(PE:EA=10:1).H NMR(400MHz,CDCl3)δ7.30–7.27(m,5H),7.19–7.12
(m,3H),7.11–7.01(m,5H),6.88–6.80(m,2H),3.37(AB,J=13.6Hz,1H),3.02(BA,J=
13
13.6Hz,1H),2.97–2.75(m,2H),2.30–2.12(m,3H),2.12–2.00(m,1H). C NMR(100MHz,
CDCl3)δ201.2,145.7,141.2,138.6,136.5,134.6,130.8,129.8,128.6,128.5,128.3,
+
128.2,127.7,127.7,127.4,120.4,55.5,41.9,36.6,35.7,23.4.HRMS(ESI)m/z calc’d
+ +
for C27H23NNaO[M+Na]:400.1672,found 400.1664;
tetrahydro‑1H‑azepine‑3‑carbonitrile],其结构式如下:
5.3Hz,1H),3.81(d,J=7.1Hz,1H),3.58(s,2H),3.28(d,J=13.7Hz,1H),3.09(d,J=
13.7Hz,1H),2.25(s,3H).
carbonitrile],其结构式如下:
13.4Hz,1H),3.01–2.82(m,3H),2.61–2.49(m,1H),2.43–2.33(m,1H).
甲苯溶液中,室温下搅拌30分钟。接着加入反应物I(0.2mmol)和反应物II(0.4mmol,),最后
再补加1mL甲苯和H2O(15uL,0.8mmol)。80℃油浴条件下反应,至TLC监测原料反应完全(约
24h)。体系恢复至室温,旋转蒸发除去溶剂后直接进行柱层析分离,选用200‑300目的硅胶,
洗脱液选用石油醚和乙酸乙酯的混合溶剂或者使用乙酸乙酯或者二氯甲烷。对映选择性ee
由配备手性分离柱的高效液相色谱测定。
1.0,CH3CN).;Rf=0.3(PE:EA=10:1).H NMR(400MHz,C6D6)δ9.73(s,1H),7.62–7.40(m,
2H),7.23–7.09(m,3H),7.08–7.02(m,2H),6.94–6.73(m,8H),3.64(AB,J=13.5Hz,1H),
3.09(BA,J=13.5Hz,1H),2.65–2.44(m,1H),2.44–2.28(m,1H),1.98–1.80(m,1H),1.78–
13
1.64(m,2H),1.54–1.34(m,1H). C NMR(100MHz,C6D6)δ180.5,142.6,141.9,139.3,138.4,
136.4,131.7,130.7,129.2,128.50,128.46,128.1,127.9,127.5,127.4,121.9,51.3,
+ +
43.2,39.1,36.2,22.8.HRMS(ESI)m/z calc’d for C27H24N2Na[M+Na] :399.1832,found
399.1824.
carbonitrile],其结构式如下:
1.0,CH3CN).Rf=0.2(PE:EA=10:1).H NMR(400MHz,CD3COCD3)δ10.21(s,1H),7.51–7.37
(m,2H),7.36–7.28(m,3H),7.11–7.00(m,5H),7.01–6.96(m,2H),6.95–6.82(m,2H),3.55
(AB,J=13.5Hz,1H),3.22(BA,J=13.4Hz,1H),2.78–2.65(m,2H),2.29–2.16(m,5H),2.03–
13
1.87(m,2H). C NMR(100MHz,CD3COCD3)δ181.0,142.0,140.0,139.9,138.2,137.5,137.0,
131.9,131.1,129.6,129.5,128.9,128.7,128.0,127.7,122.2,51.6,43.7,38.3,36.3,
+ +
22.9,21.1.HRMS(ESI)m/z calc’d for C28H27N2[M+H]:391.2169,found 391.2174.
carbonitrile],其结构式如下:
1.0,CH3CN).Rf=0.2(PE:EA=10:1).H NMR(400MHz,CD3CN)δ9.97(br s,1H),7.45–7.26
(m,5H),7.12–7.07(m,3H),7.04(d,J=8.8Hz,2H),6.94–6.82(m,2H),6.75–6.66(m,2H),
3.70(s,3H),3.49(AB,J=13.7Hz,1H),3.16(BA,J=13.6Hz,1H),2.75–2.60(m,2H),2.29–
13
2.12(m,2H),1.96–1.86(m,2H). C NMR(100MHz,CD3CN)δ181.4,159.7,142.2,140.1,
137.5,137.1,135.0,131.9,131.2,131.1,129.0,128.9,128.2,127.9,122.6,114.3,55.8,
+ +
51.7,43.7,37.9,36.2,22.8.HRMS(ESI)m/z calc’d for C28H27N2O[M+H] :407.2118,
found 407.2116.
carbonitrile],其结构式如下:
1.0,CH3CN).Rf=0.4(PE:EA=5:1).H NMR(400MHz,CD3CN)δ10.04(s,1H),7.44–7.26(m,
5H),7.19–7.14(m,2H),7.14–7.05(m,5H),6.96–6.79(m,2H),3.50(AB,J=13.6Hz,1H),
13
3.17(BA,J=13.6Hz,1H),2.73–2.60(m,2H),2.22–2.13(m,2H),2.00–1.87(m,2H). C NMR
(100MHz,CD3CN)δ180.6,141.9,141.5,139.5,138.8,137.0,133.2,131.9,131.4,131.1,
+
129.02,129.00,128.95,128.2,122.6,52.0,43.4,38.4,36.2,22.9.HRMS(ESI)m/z calc’
+ +
d for C27H24N2Cl[M+H]:411.1623,found 411.1633;
carbonitrile],其结构式如下:
1.0,CH3CN).Rf=0.3(PE:EA=10:1).H NMR(400MHz,CD3CN)δ10.04(s,1H),7.45–7.24(m,
7H),7.17–7.06(m,3H),7.02(d,J=8.5Hz,2H),6.96–6.80(m,2H),3.50(AB,J=13.5Hz,
13
1H),3.16(BA,J=13.6Hz,1H),2.73–2.61(m,2H),2.27–2.12(m,2H),2.01–1.88(m,2H). C
NMR(100MHz,CD3CN)δ180.6,142.4,141.5,139.4,138.8,137.0,132.0,131.9,131.7,
131.1,129.03,128.97,128.2,128.2,122.6,121.4,52.0,43.5,38.4,36.2,23.0.HRMS(ESI
+ +
)m/z calc’d for C27H24N2Br[M+H]:455.1118,found 455.1106.
tetrahydro‑1H‑azepine‑3‑carbonitrile],其结构式如下:
4.09(d,J=5.3Hz,1H),3.84(d,J=7.1Hz,1H),3.64(s,2H),3.32(d,J=13.7Hz,1H),3.07
(d,J=13.7Hz,1H),2.17(s,3H).
terphenyl]‑4'‑carbonitrile],其结构式如下:
(d,J=14.0Hz,1H),3.24–3.16(m,2H),2.83(dt,J=19.6,4.6Hz,1H),2.29(dt,J=13.7,
4.6Hz,1H),2.12–2.01(m,1H).
实施和局限于已报道所得产品。所属技术领域的技术人员应该明了,对本发明的任何改进,
对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,以及基于本发明
中已报到产品骨架的修饰改造,均落在本发明的保护范围和公开范围之内。