Asymmetric Synthesis of (1,5)Naphthalenophanes by Dehydro-Diels-Alder Reaction

作者：Wessig Pablo^*; Matthes Annika; Schilde Uwe; Kelling Alexandra

来源：European Journal of Organic Chemistry, 2013, (11): 2123-2129.

DOI：10.1002/ejoc.201201594

• Synthetic methods
• Macrocycles
• Cyclophanes
• Atropisomerism
• Chiral auxiliaries
• Density functional calculations

An asymmetric variant of the dehydro-Diels-Alder (DDA) reaction has been developed and applied in the atropselective synthesis of various (1,5)naphthalenophanes. Whereas the suitability of the photochemically induced DDA (PDDA) was limited, the thermally induced DDA provided the desired product, depending on the chiral auxiliary used and the length of the linker, with nearly perfect stereoselectivity. Furthermore, the mechanism of the DDA was investigated by means of DFT calculations, and a stepwise mechanism involving 1,4-biradicals was suggested.

• 出版日期2013-4