Details

Autor(en) / Beteiligte

• Liu, Yangbin
• Hu, Haipeng
• Lin, Lili
• Hao, Xiaoyu
• Liu, Xiaohua
• Feng, Xiaoming

Titel

Enantioselective construction of branched 1,3-dienyl substituted quaternary carbon stereocenters by asymmetric allenyl Claisen rearrangementElectronic supplementary information (ESI) available. CCDC 1479692 (2g) and 1480048 (E-4). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6cc06481g

Erscheinungsjahr

2016-09

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The availability of enantiomerically enriched 1,3-dienyl substituted quaternary stereocenters is highly valuable for the synthesis of complex natural compounds. Despite great advances in the area of construction of alkenyl-substituted types, a general, practical catalytic system that works for enantioselective formation of 1,3-diene derivatives still remains to be developed. Herein, we disclose the first asymmetric Claisen rearrangement of allenyl vinyl ethers to access optically active β-ketoesters, containing branched 1,3-butadienyl substituted stereocenters. A variety of substrates bearing a range of useful functional groups were well tolerated, thus affording the corresponding products with excellent enantioselectivities (up to 99% ee) and high yields (up to 91%). The enantioselective Claisen rearrangement of allenyl vinyl ethers was realized to access branched 1,3-dienyl-substituted all-carbon quaternary stereocenters using a Ni II - N , N ′-dioxide complex.