CN116239573A - 一种金属有机四元环状化合物的制备方法及其应用 - Google Patents
一种金属有机四元环状化合物的制备方法及其应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Organic Chemistry (AREA)
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Abstract
本发明属于精细化工技术领域,一种金属有机四元环状化合物的制备方法及其应用,其中制备方法,是以过渡金属镍盐中的Ni2+作为节点,以L作为配体反应制得金属有机四元环状化合物,其合成路线如下:Ni2++L→Ni‑L;本发明制备的金属有机四元环状化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中,在光照温和的条件下,高效催化苯亚甲基丙二腈制3‑苯基环氧乙烷‑2,2‑二甲腈及2‑(4‑氟亚苄基)丙二腈制3‑(4‑氟苯基)环氧乙烷‑2,2‑二甲腈方面中的应用。结果表明,苯亚甲基丙二腈有87%转化为3‑苯基环氧乙烷‑2,2‑二甲腈,2‑(4‑氟亚苄基)丙二腈有82%转化为3‑(4‑氟苯基)环氧乙烷‑2,2‑二甲腈。
Description
技术领域
本发明涉及一种金属有机四元环状化合物的制备方法及其应用,属于精细化工技术领域。
背景技术
烯烃是最重要的化工基础原料之一,对其进行绿色化深度加工,生成高附加值的化学产品具有很重要的意义。氧化反应是利用烯烃的重要途径,可使其转化为醇类、醛类、酮类、酸类和环氧化合物等含氧化合物,这些化合物具有丰富的氧官能团,可继续转变为种类繁多的精细化学品。其中,环氧化合物因其较为活泼的三元氧环结构,容易发生开环反应,或与含醇、胺等官能团的化合物作用,广泛应用于精细化学品、食品添加剂、药物中间体和化学农药生产等领域。例如环氧丙烷主要用于制造聚醚多元醇、丙二醇等化工原料,聚醚多元醇可用于生产聚氨酯泡沫,在汽车、家具、家电等领域有着广泛应用。环氧丙醇(又名缩水甘油,缩写为GLD)由于具有简单的甘油骨架和特殊的结构及能团,可以用来合成一系列治疗心血管疾病的一阻断剂、治疗艾滋病的HIV蛋白酶抑制剂、抗病毒药物及许多内酯和甘油磷脂,还可作为某些光电材料和功能高分子材料的重要中间体。又以氧化苯乙烯为例,它是一种常见的树脂添加剂,也是重要的医药、染料、香水中间体。此外,缺电子的β-氰基苯乙烯的环氧化合物在合成化学和药物化学中也有着广泛的用途,例如1,3-偶极环加成和区域选择性的亲核加成反应,同时也是合成各种具有丰富生物活性的杂环化合物的理想原料。因此,烯烃环氧化反应的研究与开发在学术领域与工业领域具有重要的意义。但是在目前文献报道的方法仍然存在各种缺陷,如使用昂贵的金属试剂、配体、苛刻的反应条件、有限的底物范围、延长的反应时间和较差的产率。研究发现,工业中制备环氧化物的方法主要包括:氯醇法、过氧酸法、Halcon法、Shell法等。氯醇法是较早实现的工业方法,包括氯醇化、皂化和精馏三个步骤。但该法能耗,物耗严重且污染严重。过氧酸法是以过氧酸为氧化剂直接氧化烯烃为环氧化物的方法,但是过氧酸价格较高,同时存在污染问题。Halcon法和Shell法则是利用不同的催化剂和过氧化氢为氧化剂制备环氧化合物的方法,此方法生产成本加大,且得到较多副产品。生产过程较为复杂,基础建设投资过大。
发明内容
为了克服现有技术中存在的不足,本发明目的是提供一种金属有机四元环状化合物的制备方法及其应用。采用该种方法制备的金属有机四元环状化合物可以利用空腔的限域作用包合缺电子烯烃化合物,同时通过修饰的NADH模型和四元环的疏水空腔可以有效模拟自然界的氧化酶,加快电子转移。利用过渡金属镍盐合成的金属有机超分子在常温可见光照射下进行光催化实现烯烃制备环氧化合物。
为了实现上述发明目的,解决现有技术存在的问题,本发明采取的技术方案是:一种金属有机四元环状化合物的制备方法,是以过渡金属镍盐中的Ni2+作为节点,以L作为配体反应制得金属有机四元环状化合物,其合成路线如下:
Ni2++L→Ni-L
所述配体L选自H2ZPC;
所述过渡金属镍盐选自高氯酸镍、硝酸镍、四氟硼酸镍或三氟甲磺酸镍中的一种;
所述配体H2ZPC具有如下(A)分子结构式,
制备方法,包括以下步骤:
步骤1、将N-Boc-乙二胺、丙炔酸甲酯和苯甲醛按照1:2~2.2:1~1.2的摩尔比加入到10~30mL冰乙酸中,在75~85℃的条件下搅拌3~4h,形成黄色固体再加入150~200mL二氯甲烷把固体全部溶解,再向其中加入50~100mL三氟乙酸,反应在室温条件下继续搅拌5~10h,减压蒸馏除去溶剂,向其中加入150~200mL异丙醇,在75~85C下回流搅拌10~12h,抽滤得到黄色滤饼,用Na2CO3水溶液溶解滤饼,并用二氯甲烷萃取,减压蒸馏,得到黄色粉末;
步骤2、将步骤1得到的黄色粉末加入到150~200mL甲苯溶液中,并加入30~50mL乙酸酐,在75~85C回流搅拌10~12h,抽滤用乙醚洗涤粗产物,真空干燥滤饼得到黄色粉末;
步骤3、将步骤2得到的黄色粉末与20~30mL乙醇和150~180mL水合肼混合,在80~90C中加热搅拌15~18h,将产物抽滤并用乙醇洗涤,真空干燥洗涤后的滤饼,得到白色粉末;
步骤4、将步骤3得到的白色粉末与吡啶-2-甲醛按照1:2.0~2.5的摩尔比加入到80~120mL乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~90C的条件下回流10~15h,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H2ZPC;
步骤5、将步骤4得到的配体H2ZPC与金属镍盐按照1:1~1.5的摩尔比加入到乙醇与三氯甲烷的混合溶剂中,室温下搅拌8~10h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色晶体,即可制得目标化合物Ni-ZPC,所述乙醇与三氯甲烷的体积比为1:0.8~1.2。
所述方法制备的金属有机四元环状化合物在催化苯亚甲基丙二腈制3-苯基环氧乙烷-2,2-二甲腈及2-(4-氟亚苄基)丙二腈制3-(4-氟苯基)环氧乙烷-2,2-二甲腈方面中的应用。
本发明有益效果是:一种金属有机四元环状化合物的制备方法及其应用,其中制备方法,是以过渡金属镍盐中的Ni2+作为节点,以L作为配体反应制得金属有机四元环状化合物,其合成路线如下:Ni2++L→Ni-L;与已有技术相比,采用该方法制备的金属有机四元环状化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中,并且可在光照温和的条件下,高效催化苯亚甲基丙二腈制3-苯基环氧乙烷-2,2-二甲腈及2-(4-氟亚苄基)丙二腈制3-(4-氟苯基)环氧乙烷-2,2-二甲腈方面中的应用。结果表明,苯亚甲基丙二腈有87%转化为3-苯基环氧乙烷-2,2-二甲腈,2-(4-氟亚苄基)丙二腈有82%转化为3-(4-氟苯基)环氧乙烷-2,2-二甲腈。
附图说明
图1是本发明实施例1目标化合物Ni-ZPC的晶体结构图。
图2是本发明实施例1目标化合物Ni-ZPC溶液的高分辨质谱图。
图3是本发明实施例5目标化合物Ni-ZPC光照条件下催化苯亚甲基丙二腈制3-苯基环氧乙烷-2,2-二甲腈的反应产率随时间变化曲线图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
将N-Boc-乙二胺(100mmol,16.0g)、丙炔酸甲酯(200mmol,16.8g)和苯甲醛(100mmol,10.6g)加入到20mL冰乙酸中,在80C的条件下搅拌4h,形成黄色固体,加入200mL二氯甲烷把固体全部溶解,再向其中加入100mL三氟乙酸,反应在室温条件下继续搅拌8h,减压蒸馏除去溶剂,向其中加入200mL异丙醇,在80C下回流搅拌12h,抽滤得到黄色滤饼,用Na2CO3水溶液溶解滤饼,并用二氯甲烷萃取,减压蒸馏,得到黄色粉末(20.1g,产率63.6%)。1H-NMR(400MHz,Chloroform-d)δ7.35-7.26(m,3H),7.25-7.21(m,3H),7.18-7.12(m,1H),4.90(s,1H),3.63(s,6H),3.46(t,J=6.0Hz,2H),3.02(t,J=6.0Hz,2H).
称取黄色粉末(50mmol,15.8g)加入到150mL甲苯溶液中,并加入50mL乙酸酐,在80C回流搅拌12h,抽滤用乙醚洗涤粗产物,真空干燥滤饼得到黄色粉末(17.5g,产率97.8%)。1H-NMR(400MHz,Chloroform-d)δ7.30-7.27(m,2H),7.24(d,J=8.0Hz,2H),7.20(s,2H),7.18-7.12(m,1H),5.74(s,1H),4.90(s,1H),3.63(s,6H),3.59-3.54(m,2H),3.48(q,J=5.9Hz,2H),1.99(s,3H).
将上述得到的黄色粉末(25mmol,9.0g)与20mL乙醇和150mL水合肼混合,在85C中加热搅拌15h,将产物抽滤并用乙醇洗涤,真空干燥洗涤后的滤饼,得到白色粉末(4.0g,产率52.5%);1H-NMR(400MHz,DMSO-d6)δ8.61(s,2H),7.92(t,J=5.5Hz,1H),7.25-7.15(m,4H),7.12-7.04(m,3H),4.96(s,1H),4.11(s,4H),3.43(t,J=6.2Hz,2H),3.28(q,J=6.0Hz,2H),1.81(s,3H).
将白色粉末(10mmol,3.6g)与吡啶-2-甲醛(22mmol,2.36g)加入到100mL乙醇中混合,再加入5滴冰醋酸,将混合溶液在80C的条件下回流12h,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H2ZPC(4.83g,产率90.3%);1H-NMR(400MHz,DMSO-d6)δ11.32(s,2H),8.57(dt,J=4.9,1.3Hz,2H),8.24(s,2H),8.05(t,J=5.4Hz,1H),7.92-7.79(m,4H),7.42-7.33(m,4H),7.33-7.27(m,2H),7.23(t,J=7.6Hz,2H),7.15-7.07(m,1H),5.28(s,1H),3.57(t,J=6.2Hz,2H),3.40(t,J=5.9Hz,2H),1.84(s,3H).ESI-MS calcd for C29H28N8O3 536.2284,found 537.2357[M+H]+,559.2177[M+Na]+。
称取配体H2ZPC(0.05mmol,26.8mg)与Ni(BF4)2·6H2O(0.075mmol,27.5mg)加入到30mL体积比为1:1的乙醇与三氯甲烷的混合溶剂中,室温下搅拌8h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色固体,即可制得目标化合物Ni-ZPC(43.8mg,产率58.4%)。晶体结构图,如图1所示。ESI-MS:m/z:1187.3050[H2Ni4(ZPC)4]2+,1231.3094[H2Ni4(ZPC)4·BF4]2+。化合物Ni-ZPC溶液的高分辨质谱图,如图2所示。
实施例2
称取配体H2ZPC(0.05mmol,26.8mg)与Ni(NO3)2·6H2O(0.075mmol,21.8mg)加入到30mL体积比为1:1的乙醇与三氯甲烷的混合溶剂中,室温下搅拌8h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色固体,即可制得目标化合物Ni-ZPC(38.1mg,产率50.8%)。ESI-MS:m/z:791.8731[H3Ni4(ZPC)4]3+。
实施例3
称取配体H2ZPC(0.05mmol,26.8mg)与Ni(ClO4)2·6H2O(0.075mmol,27.4mg)加入到30mL体积比为1:1的乙醇与三氯甲烷的混合溶剂中,室温下搅拌8h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色固体,即可制得目标化合物Ni-ZPC(35.1mg,产率46.8%)。ESI-MS:m/z:791.8731[H3Ni4(ZPC)4]3+。
实施例4
称取配体H2ZPC(0.05mmol,26.8mg)与Ni(CF3SO3)2·6H2O(0.075mmol,26.8mg)加入到30mL体积比为1:1的乙醇与三氯甲烷的混合溶剂中,室温下搅拌8h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色固体,即可制得目标化合物Ni-ZPC(31.5mg,产率42%)。ESI-MS:m/z:791.8731[H3Ni4(ZPC)4]3+。
实施例5利用Ni-ZPC催化苯亚甲基丙二腈制3-苯基环氧乙烷-2,2-二甲腈
在10mL的光反应管中,先加入5mL乙腈溶液,然后依次加入1.2mg的Ru(bpy)3(PF6)2,1.5mg Ni-ZPC,15.4mg苯亚甲基丙二腈和50μL三乙醇胺。用封口塞密封,通入十分钟氧气排除其它气体干扰,通气结束后在光反应管上连接氧气球以保证氧气供应,在455nm波段灯下光照12小时,反应结束后,利用1,3,5-三甲氧基苯作为内标来计算产率,结果苯亚甲基丙二腈有87%转化为3-苯基环氧乙烷-2,2-二甲腈,选择性大于99%,如图3所示。
实施例6利用Ni-ZPC催化2-(4-氟亚苄基)丙二腈制3-(4-氟苯基)环氧乙烷-2,2-二甲腈
在10mL的光反应管中,先加入5mL乙腈溶液,然后依次加入1.2mg的Ru(bpy)3(PF6)2,1.5mg Ni-ZPC,17.2mg 2-(4-氟亚苄基)丙二腈和50μL三乙醇胺。用封口塞密封,通入十分钟氧气排除其它气体干扰,通气结束后在光反应管上连接氧气球以保证氧气供应,在455nm波段灯下光照12小时,反应结束后,利用1,3,5-三甲氧基苯作为内标来计算产率,结果2-(4-氟亚苄基)丙二腈有82%转化为3-(4-氟苯基)环氧乙烷-2,2-二甲腈,选择性大于99%。
本发明优点在于:采用该方法制备的金属有机四元环原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中。作为一种催化剂在光照条件下原位催化氧化烯烃环氧化,具有很高的催化转化效率。
Claims (2)
1.一种金属有机四元环状化合物的制备方法,其特征在于:以过渡金属镍盐中的Ni2+作为节点,以L作为配体反应制得金属有机四元环状化合物,其合成路线如下:
Ni2++L→Ni-L
所述配体L选自H2ZPC;
所述过渡金属镍盐选自高氯酸镍、硝酸镍、四氟硼酸镍或三氟甲磺酸镍中的一种;
所述配体H2ZPC具有如下(A)分子结构式,
制备方法,包括以下步骤:
步骤1、将N-Boc-乙二胺、丙炔酸甲酯和苯甲醛按照1:2~2.2:1~1.2的摩尔比加入到10~30mL冰乙酸中,在75~85℃的条件下搅拌3~4h,形成黄色固体再加入150~200mL二氯甲烷把固体全部溶解,再向其中加入50~100mL三氟乙酸,反应在室温条件下继续搅拌5~10h,减压蒸馏除去溶剂,向其中加入150~200mL异丙醇,在75~85℃下回流搅拌10~12h,抽滤得到黄色滤饼,用Na2CO3水溶液溶解滤饼,并用二氯甲烷萃取,减压蒸馏,得到黄色粉末;
步骤2、将步骤1得到的黄色粉末加入到150~200mL甲苯溶液中,并加入30~50mL乙酸酐,在75~85℃回流搅拌10~12h,抽滤用乙醚洗涤粗产物,真空干燥滤饼得到黄色粉末;
步骤3、将步骤2得到的黄色粉末与20~30mL乙醇和150~180mL水合肼混合,在80~90℃中加热搅拌15~18h,将产物抽滤并用乙醇洗涤,真空干燥洗涤后的滤饼,得到白色粉末;
步骤4、将步骤3得到的白色粉末与吡啶-2-甲醛按照1:2.0~2.5的摩尔比加入到80~120mL乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~90℃的条件下回流10~15h,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H2ZPC;
步骤5、将步骤4得到的配体H2ZPC与金属镍盐按照1:1~1.5的摩尔比加入到乙醇与三氯甲烷的混合溶剂中,室温下搅拌8~10h,搅拌过滤后,将滤液静置于室温下2周后溶液中析出橙黄色晶体,即可制得目标化合物Ni-ZPC,所述乙醇与三氯甲烷的体积比为1:0.8~1.2。
2.根据权利要求1所述方法制备的金属有机四元环状化合物在催化苯亚甲基丙二腈制3-苯基环氧乙烷-2,2-二甲腈及2-(4-氟亚苄基)丙二腈制3-(4-氟苯基)环氧乙烷-2,2-二甲腈方面中的应用。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103724255A (zh) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | 一类用于检测爆炸物rdx的基于酰胺基二氢吡啶结构的化合物制备方法 |
CN110483585A (zh) * | 2019-07-26 | 2019-11-22 | 大连理工大学 | 一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用 |
CN111019644A (zh) * | 2019-12-16 | 2020-04-17 | 大连理工大学 | 辅因子-底物探针平台用于肿瘤缺氧相关酶的快速定量检测 |
CN111454249A (zh) * | 2020-04-23 | 2020-07-28 | 大连理工大学 | 一种金属有机笼状化合物的制备方法及其应用 |
-
2023
- 2023-02-14 CN CN202310109316.3A patent/CN116239573B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103724255A (zh) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | 一类用于检测爆炸物rdx的基于酰胺基二氢吡啶结构的化合物制备方法 |
CN110483585A (zh) * | 2019-07-26 | 2019-11-22 | 大连理工大学 | 一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用 |
CN111019644A (zh) * | 2019-12-16 | 2020-04-17 | 大连理工大学 | 辅因子-底物探针平台用于肿瘤缺氧相关酶的快速定量检测 |
CN111454249A (zh) * | 2020-04-23 | 2020-07-28 | 大连理工大学 | 一种金属有机笼状化合物的制备方法及其应用 |
Non-Patent Citations (5)
Title |
---|
: MIRHASHEMI, F. 等: "Epoxidation of vinyl cyanides by calcium hypochlorite under catalyst- and solvent-free conditions", TETRAHEDRON LETTERS, vol. 59, no. 27, 31 December 2018 (2018-12-31), pages 2661 - 2663, XP085405185, DOI: 10.1016/j.tetlet.2018.05.077 * |
MANGAONKAR, SAEESH R. 等: "Hypervalent Iodine(III)-Catalyzed Epoxidation of β-Cyanostyrenes", SYNTHESIS, vol. 51, no. 23, 31 December 2019 (2019-12-31), pages 4473 - 4486 * |
WEI, JIANWEI 等: "Light-switched selective catalysis with NADH mimic functionalized metal-organic capsules", CHEMICAL COMMUNICATIONS, vol. 59, no. 01, 2 December 2022 (2022-12-02), pages 71 - 74 * |
WEI, JIANWEI 等: "Metal-Organic Capsules with NADH Mimics as Switchable Selectivity Regulators for Photocatalytic Transfer Hydrogenation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 141, no. 32, 31 December 2019 (2019-12-31), pages 12707 - 12716 * |
ZHAO, LIANG 等: "Renewable Molecular Flasks with NADH Models: Combination of Light-Driven Proton Reduction and Biomimetic Hydrogenation of Benzoxazinones", ANGEWANDTE CHEMIE, vol. 56, no. 30, 31 December 2017 (2017-12-31), pages 8692 - 8696 * |
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