投稿范围：煤(mei)化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、盐化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、生(sheng)物化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、医药化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、石(shi)油化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、农用(yong)化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)环保、工(gong)(gong)(gong)(gong)业水处(chu)理、精(jing)细化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、日用(yong)化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、燃(ran)气化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)、橡胶(jiao)与(yu)轮(lun)胎工(gong)(gong)(gong)(gong)业、化(hua)(hua)(hua)(hua)(hua)(hua)肥农药、有机(ji)与(yu)无机(ji)、涂料与(yu)油墨、染料与(yu)颜料、助(zhu)剂与(yu)添(tian)加剂、树脂与(yu)塑料、胶(jiao)粘(zhan)剂、化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)教育、化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)设计、化(hua)(hua)(hua)(hua)(hua)(hua)工(gong)(gong)(gong)(gong)机(ji)械(xie)与(yu)装备(bei)
近日，中国科学技术大学合肥微尺度物质科学国家研究中心、化学与材料科学学院教授傅尧与特任副研究员陆熹在手性胺合成领域取得进展，开发镍氢催化烯酰胺不对称氢烷基化，实现温和条件手性脂肪胺模块化合成。2月26日，相关研究成果于以Catalytic asymmetric reductive hydroalkylation of enamides and enecarbamates to chiral aliphatic amines为题，发(fa)表在《自然·通讯(xun)》上。
手(shou)(shou)(shou)性(xing)(xing)胺是(shi)重要的(de)手(shou)(shou)(shou)性(xing)(xing)助剂以及医药、天然产物(wu)的(de)关(guan)键合成(cheng)(cheng)中(zhong)(zhong)间体。2019年零售额前200名的(de)药物(wu)中(zhong)(zhong)，超过三成(cheng)(cheng)都(dou)含有(you)手(shou)(shou)(shou)性(xing)(xing)胺结构(gou)。高效、便捷(jie)合成(cheng)(cheng)手(shou)(shou)(shou)性(xing)(xing)胺化(hua)合物(wu)是(shi)有(you)机(ji)合成(cheng)(cheng)化(hua)学研究的(de)重要方(fang)向。常(chang)规催化(hua)合成(cheng)(cheng)手(shou)(shou)(shou)段，如亚胺/烯胺氢(qing)(qing)化(hua)、亚胺烷基化(hua)、烯烃氢(qing)(qing)胺化(hua)等，在(zai)(zai)双烷基取代(dai)手(shou)(shou)(shou)性(xing)(xing)脂(zhi)肪胺合成(cheng)(cheng)中(zhong)(zhong)存(cun)在(zai)(zai)底物(wu)结构(gou)局限。
科研人员提出“烯烃还原偶联”概念，开发廉价金属镍催化体系，以烯烃替代当量金属试剂实现温和条件碳-碳偶联，简化合成步骤、丰富底物范围、提升官能团兼容性 （Nat. Commun. 2016,7, 11129;J. Am. Chem. Soc. 2017,139, 12632;J. Am. Chem. Soc. 2020,142, 214）。近期(qi)，科(ke)研(yan)人员在饱和碳(tan)偶(ou)联合(he)成手(shou)(shou)(shou)性(xing)(xing)(xing)胺(an)方向取得进展，成功实现镍(nie)氢催(cui)化(hua)(hua)烯酰(xian)胺(an)不(bu)对称氢烷基(ji)化(hua)(hua)。反应(ying)使用(yong)(yong)性(xing)(xing)(xing)质稳定、易(yi)于获取的(de)烯酰(xian)胺(an)与(yu)烷基(ji)卤(lu)化(hua)(hua)物(wu)(wu)(wu)为(wei)原料(liao)，高对映选择性(xing)(xing)(xing)制(zhi)备酰(xian)基(ji)保护的(de)手(shou)(shou)(shou)性(xing)(xing)(xing)脂(zhi)肪胺(an)化(hua)(hua)合(he)物(wu)(wu)(wu)，反应(ying)条件温(wen)和、底物(wu)(wu)(wu)适用(yong)(yong)范围广。反应(ying)可应(ying)用(yong)(yong)于多种天然产物(wu)(wu)(wu)、药物(wu)(wu)(wu)分子(zi)高效合(he)成和修(xiu)饰(shi)。例如，反应(ying)可以实现生(sheng)(sheng)物(wu)(wu)(wu)碱毒芹碱、多动症药物(wu)(wu)(wu)利地(di)美、哮喘药物(wu)(wu)(wu)卡莫(mo)特罗(luo)等生(sheng)(sheng)理(li)活性(xing)(xing)(xing)分子(zi)或其同位素(su)标记物(wu)(wu)(wu)的(de)高效合(he)成。此外，反应(ying)还可实现烯酰(xian)胺(an)与(yu)α-硼酸(suan)酯(zhi)卤(lu)化(hua)(hua)物(wu)(wu)(wu)的(de)不(bu)对称氢烷基(ji)化(hua)(hua)，制(zhi)备具(ju)有(you)(you)两个手(shou)(shou)(shou)性(xing)(xing)(xing)中心的(de)β-胺(an)基(ji)硼酸(suan)酯(zhi)。新方法串联有(you)(you)机含硼化(hua)(hua)合(he)物(wu)(wu)(wu)丰富(fu)的(de)转化(hua)(hua)，如氧(yang)化(hua)(hua)和芳基(ji)化(hua)(hua)等，将有(you)(you)助于开发复杂(za)结构(gou)的(de)胺(an)类手(shou)(shou)(shou)性(xing)(xing)(xing)分子(zi)。
该研究(jiu)(jiu)展示了一种镍催化饱和(he)碳偶(ou)联模块化合成(cheng)手性(xing)脂肪(fang)胺的(de)新(xin)(xin)策(ce)略，为含(han)手性(xing)胺结构药物、天然(ran)产(chan)物和(he)含(han)氮复杂手性(xing)分子合成(cheng)提(ti)供了新(xin)(xin)方法，是(shi)常规手性(xing)胺合成(cheng)策(ce)略结构局限的(de)补充与(yu)突破。中(zhong)(zhong)国(guo)科(ke)大化学(xue)(xue)与(yu)材(cai)料科(ke)学(xue)(xue)学(xue)(xue)院(yuan)博士研究(jiu)(jiu)生(sheng)王加旺和(he)合肥微(wei)尺度(du)物质(zhi)科(ke)学(xue)(xue)国(guo)家研究(jiu)(jiu)中(zhong)(zhong)心博士研究(jiu)(jiu)生(sheng)李炎(yan)为论文共同(tong)第一作者(zhe)。研究(jiu)(jiu)工作得到国(guo)家自然(ran)科(ke)学(xue)(xue)基金委员会、中(zhong)(zhong)国(guo)科(ke)学(xue)(xue)院(yuan)和(he)安徽省生(sheng)物质(zhi)洁净能源重点(dian)实验室的(de)支持。