Alkali-metal-mediated manganationII of functionalized arenes and applications of ortho-manganated products in Pd-catalyzed cross-coupling reactions with iodobenzene.
Alkali-metal-mediated manganationII of functionalized arenes and applications of ortho-manganated products in Pd-catalyzed cross-coupling reactions with iodobenzene.
复制标题
碱金属介导的功能化领域的锰和正形产物在与碘苯苯二催化的交叉偶联反应中的应用。
DOI：
10.1002/chem.200701597
复制
发表时间：
2008
影响因子：
4.3
通讯作者：
Russo, Luca
中科院分区：
文献类型：
--
作者：
Blair, Victoria L.;Clegg, William;Conway, Ben;Hevia, Eva;Kennedy, Alan;Klett, Jan;Mulvey, Robert E.;Russo, Luca
将最近引入的“碱金属介导的锰化”概念扩展到官能化芳烃，杂感锰酸钠试剂[(Tmeda)Na(TMP)(R)Mn(TMP)](1；TMEDA=N，N，N‘，N’-四甲基乙二胺，TMP=2，2，6，6-四甲基吡啶，R=CH2 SiMe3)在己烷中以1：1的化学计量比与苯甲醚或N，N-二异丙基苯甲酰胺反应。X-射线单晶研究表明，这些反应生成了晶体[(Tmeda)Na(TMP)(o-C6H4OMe)Mn(TMP)](2)和[(tmeda)Na(tmp){o-{C(O)N(iPr)2C6H4}Mn(CH2SiMe3)](3)。根据这些产物，可以推测试剂1在第一反应中至少部分并最终作为烷基碱释放硅烷Me4Si，但在第二反应中作为酰胺碱释放胺TMPH。这两个顺磁产物2和3都具有接触离子对结构，其主要特征分别是六原子五元(NaNMnCCO)和七原子五元(NaNMnCCCO)环。在[PdCl2(Dppf)](dppf=1，1‘-双(二苯基膦)二茂铁)催化下，锰酸盐2和3分别与碘苯发生交叉偶联反应生成不对称联芳烃，产率分别为98.0%和66.2%。强调碱金属中间体在这些锰化反应中的重要性，双烷基锰试剂本身不能金属化所述苯甲酰胺，而是生成单体给体-受体络合物[Mn(R)2{(IPR)2NC(Ph)(=O)}2](5)，并对其进行了结晶学表征。在一次重复合成2的尝试中，得到了被丁氧基污染的配合物[{(Tmeda)Na(R)(OBU)(o-C6H4OMe)Mn}2](6)。与2和3相反，由于空间约束减少，该配合物在晶体中采用二聚体排列，其中心是一个12个原子的(NaOCCMnC)2环。
Extending the recently introduced concept of “alkali-metal-mediated manganation” to functionalised arenes, the heteroleptic sodium manganate reagent [(tmeda)Na(tmp)(R)Mn(tmp)] (1; TMEDA = N,N,N′,N′-tetra-methylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidide, R = CH2 SiMe3) has been treated with anisole or N,N-diisopropylbenzamide in a 1:1 stoichiometry in hexane. These reactions afforded the crystalline products [(tmeda)Na(tmp)(o-C6H4OMe)Mn(tmp)] (2) and [(tmeda)Na(tmp){o-{C(O)N(iPr)2C6H4}Mn(CH2SiMe3)] (3), respectively, as determined from X-ray crystallographic studies. On the basis of these products, it can be surmised that reagent 1 has acted, at least partially and ultimately, as an alkyl base in the first reaction liberating the silane Me4Si, but as an amido base in the second reaction liberating the amine TMPH. Both of these paramagnetic products 2 and 3 have contacted ion-pair structures, the key features of which are six-atom, five-element (NaNMnCCO) and seven-atom, five-element (NaNMnCCCO) rings, respectively. Manganates 2 and 3 were successfully cross-coupled with iodobenzene under [PdCl2(dppf)] (dppf=1,1′-bis(diphenylphosphino)ferrocene) catalysis to generate unsymmetrical biaryl compounds in yields of 98.0 and 66.2%, respectively. Emphasizing the importance of alkali-metal mediation in these manganation reactions, the bisalkyl Mn reagent on its own fails to metalate the said benzamide, but instead produces the monomeric, donor–acceptor complex [Mn(R)2{(iPr)2NC(Ph)(=O)}2] (5), which has also been crystallographically characterised. During one attempt to repeat the synthesis of 2, the butoxide-contaminated complex [{(tmeda)Na(R)(OBu)(o-C6H4OMe)Mn}2] (6) was obtained. In contrast to 2 and 3, due to reduced steric constraints, this complex adopts a dimeric arrangement in the crystal, the centrepiece of which is a twelve atom (NaOCCMnC)2 ring.
登录
查看更多内容
影响因子：
4.9
作者：
Gallagher, DJ;Henderson, KW;Rowlings, RB
通讯作者：
Rowlings, RB
影响因子：
16.6
作者：
Garcia-Alvarez, Joaquin;Kennedy, Alan R.;Mulvey, Robert E.
通讯作者：
Mulvey, Robert E.
DOI：
10.1002/9783527619467.ch13
发表时间：
2005-01-01
期刊：
HANDBOOK OF FUNCTIONALIZED ORGANOMETALLICS: APPLICATIONS IN SYNTHESIS
影响因子：
--
作者：
Cahiez, Gerard;Mahuteau-Betzer, Florence
通讯作者：
Mahuteau-Betzer, Florence
影响因子：
4.9
作者：
Drewette, KJ;Henderson, KW;Rowlings, RB
通讯作者：
Rowlings, RB
影响因子：
2.8
作者：
Gren, Cameron K.;Hanusa, Timothy P.;Rheingold, Arnold L.
通讯作者：
Rheingold, Arnold L.