Departamento de Química Orgánica y Centro Singular de Investigación en Química Biológica y Materiales Moleculares (CIQUS), Universidad de Santiago de Compostela, 15782 Santiago de Compostela (Spain) http://www.usc.es/gi1603/saa.
Angew Chem Int Ed Engl. 2015 Feb 23;54(9):2724-8. doi: 10.1002/anie.201410284. Epub 2015 Jan 16.
A new ruthenium-catalyzed cyclization of ortho-(alkynyloxy)benzylamines to dihydro-1,3-benzoxazines is reported. The cyclization is thought to take place via the vinyl ruthenium carbene intermediates which are easily formed from [Cp*RuCl(cod)] and N2 CHSiMe3 . The mild reaction conditions and the efficiency of the procedure allow the easy preparation of a broad range of new 2-vinyl-2-substituted 1,3-benzoxazine derivatives. Rearrangement of an internal C(sp) in the starting material into a tetrasubstituted C(sp(3) ) atom in the final 1,3-benzoxazine is highly remarkable.
报道了一种新型的钌催化邻（炔氧基）苄胺的二氢-1,3-苯并恶嗪的环化反应。该环化反应被认为是通过[Cp*RuCl(cod)]和 N2 CHSiMe3 容易形成的乙烯基钌卡宾中间体发生的。温和的反应条件和高效的反应过程允许广泛的新型 2-乙烯基-2-取代 1,3-苯并恶嗪衍生物的简便制备。起始原料中的内部 C(sp)重排到最终 1,3-苯并恶嗪中的四取代 C(sp(3) )原子是非常显著的。
