The N,N′-dioxide/Ni(ii)-catalyzed asymmetric inverse-electron-demand hetero-Diels-Alder reaction of methyleneindolinones with hetero-substituted alkenesElectronic supplementary information (ESI) available. CCDC 1056433. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cc04245c

The highly efficient catalytic asymmetric inverse-electron-demand hetero-Diels-Alder reaction of methyleneindolinones with hetero-substituted alkenes has been accomplished under mild reaction conditions. In the presence of chiral N , N ′-dioxide/Ni( ii ) complexes, a wide range of optically active dihydropyran-fused indoles were obtained in up to 99% yield, >95 : 5 dr and 99% ee. The asymmetric inverse-electron-demand hetero-Diels-Alder reaction of methyleneindolinones with hetero-substituted alkenes catalyzed by chiral N , N ′-dioxide/Ni( ii ) complexes has been accomplished, affording dihydropyran-fused indoles in up to 99% yield, >95 : 5 dr and 99% ee.