Stereoelectronic Effects on Dienophile Separation Influence the Diels–Alder Synthesis of Molecular Clefts. Issue 45 (4th December 2017)

• Record Type: Journal Article
• Authors: Stoermer, Martin J.; Wickramasinghe, Wasantha A.; Byriel, Karl A.; Hockless, David C. R.; Skelton, Brian W.; Sobolev, Alexandre N.; White, Allan H.; Mak, Jeffrey Y. W.; Fairlie, David P.
• Is Part Of: European journal of organic chemistry. Issue 45(2017)
• Page Start: 6793
• Page End: 6796
• Publication Date: 2017-12-04
• Subjects: Diene -- Cavity -- Host‐guest systems -- Solid‐state structures -- Pi interactions; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201701319
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The formal cycloaddition adduct of 1, 4‐benzoquinone with two equivalents of cyclopentadiene is a scaffold with two non‐conjugated alkenes. Both alkenes undergo endo [4+2] cycloaddition with a diene to form a rigid U‐shaped molecular cleft. Here we show experimental, computational and structural evidence that π interactions between the alkenes affect structural rigidity, Diels–Alder reactivity, cleft formation and host–guest capture. Abstract : Five crystal structures show that structural rigidity and π–π interactions strongly influence Diels–Alder [4+2] cycloadditions leading to U‐shaped clefts, one capturing a chloroform molecule within its aromatic enclave.