cis–trans Enantiomerism in the Diels–Alder cycloadducts of 6-arylfulvenes with maleic anhydride: resolution of the exo adducts via the N-((1S)-1-(naphth-1-yl)ethyl)imide derivatives: assignment of the absolute configurations based on the crystal structure of an imide diastereomer |
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| Institution: | 1. Departamento de Química Orgánica, Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain;2. Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Spain;3. Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain;4. Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco, P. K. 1072, E-20018 San Sebastián, Spain;5. IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain;1. Department of Chemistry, Periyar University, Salem 636 011, India;2. Department of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland;1. MTA-DE Homogeneous Catalysis and Reaction Mechanisms Research Group, H-4010 Debrecen, POB 7, Hungary;2. Department of Organic Chemistry, University of Debrecen, H-4010 Debrecen, POB 20, Hungary;3. Department of Physical Chemistry, University of Debrecen, H-4010 Debrecen, POB 7, Hungary;1. State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050, China;2. Sate Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050, China;3. University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049, China;4. SGS China Co., Ltd., 4F, Building 3, No. 889, Yishan Road, Shanghai 200233, China;5. School of Electronic Engineering, Bangor University, Bangor LL57 1UT, United Kingdom |
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| Abstract: | A new case of the uncommon cis–trans enantiomerism is presented. The titled anhydride adducts were prepared in good yields by the known reaction of three 6-arylfulvenes with maleic anhydride (aryl = phenyl, p-tolyl and p-anisyl). The exo adducts were converted to the corresponding imides by reaction with (1S)-1-(naphth-1-yl)ethylamine in ∼80% yields, and the resulting diastereomeric imides separated by silica gel column chromatography. They were hydrolysed and recyclised to the chiral anhydrides, in ‘one-pot’ with 10% NaOH–EtOH, followed by treatment with 2 M HCl, in ∼40% yields. The titled anhydrides were thus obtained in homochiral form, in enantiomeric purities (generally) of ∼90% as indicated by chiral HPLC. The chiral anhydrides were also converted to the corresponding imides (presumably stereospecifically), by treatment with ammonia solution in excellent yields. The crystal structure of one of the above diastereomeric imides (derived from 6-phenylfulvene) was determined, and based on the known (S)-configuration of the naphthylethylamine moiety, the ‘configurations’ of the original anhydride adducts were assigned. |
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