Distal‐Bond‐Selective C−C Activation of Ring‐Fused Cyclopentanones: An Efficient Access to Spiroindanones

• Published in: Angewandte Chemie International Edition Vol. 56; no. 9; pp. 2376 - 2380
• Main Authors: Xia, Ying, Wang, Jianbo, Dong, Guangbin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 20.02.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Activation; Catalysis; Chemistry; Chemistry, Multidisciplinary; cyclopentanones; C−C activation; homogeneous catalysis; Physical Sciences; Rhodium; Science & Technology; Selectivity; spirocycles; spirocycles; CARBON-CARBON BONDS; CLEAVAGE; ALLENES; ALKYNES; C-C activation; CYCLOBUTENONES; homogeneous catalysis; cyclopentanones; METAL-CATALYZED CYCLOADDITIONS; INDANONES; DERIVATIVES; CYCLOBUTANONES; CYCLIZATION; rhodium; C−C activation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201611642

A site‐selective rhodium‐catalyzed C−C activation of ring‐fused cyclopentanones was achieved to afford efficient access to a range of spiroindanones. The use of bulky 2‐amino‐6‐picoline as a cocatalyst is key to the excellent selectivity of this C−C bond cleavage in cyclopentanones. So far, so good: Rhodium‐catalyzed C−C activation of ring‐fused cyclopentanones was achieved site selectively for the distal over the proximal position. Key to this outcome is the combination of a bulky 2‐amino‐6‐picoline (C1) with a bulky NHC ligand. This unusual intramolecular skeleton rearrangement offers rapid access to a diverse range of spiroindanones.