Thermal reaction of electron deficient 4‐oxo‐4H‐pyrazole 1, 2‐dioxide with cycloheptatriene: the first examples of the formation of an endo‐[4π + 6π]‐cycloadduct and an intramolecular 1, 3‐dipolar reaction leading to a heterocage. (6th November 2012)

• Record Type: Journal Article
• Authors: Yamaguchi, Koki; Eto, Masashi; Yoshitake, Yasuyuki; Harano, Kazunobu
• Is Part Of: Journal of physical organic chemistry. Volume 26:Number 1(2013:Jan.)
• Page Start: 64
• Page End: 69
• Publication Date: 2012-11-06
• Subjects: 1, 3‐dipolar cycloaddition -- 4‐oxo‐4H‐pyrazole 1, 2‐dioxide -- heterocage -- endo‐[4π + 6π] cycloaddition -- bond elongation -- DFT calculation; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3066
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract : The reaction of 3, 5‐bis(methoxycarbonyl)‐4‐oxo‐4 H ‐pyrazole 1, 2‐dioxide (1a) with 1, 3, 5‐cycloheptatriene (2b) gave a mixture of the novel endo ‐[4 + 6]‐cycloadduct (4ab), anti‐exo ‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1, 3‐dipolar cycloaddition reaction of the syn‐endo ‐[4 + 2]‐cycloadduct. Analogous endo ‐[4 + 6] selectivity in 1, 3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long N sp3 –Ns p3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd. Abstract : The reaction of 3, 5‐bis(methoxycarbonyl)‐4‐oxo‐4 H ‐pyrazole 1, 2‐dioxide with 1, 3, 5‐cycloheptatriene gave a mixture of the novel endo ‐[4+6]‐cycloadduct, anti‐exo ‐[4+2]‐cycloadduct and the heterocage derived from the intramolecular 1, 3‐dipolar cycloaddition reaction of the syn‐endo ‐[4+2]‐cycloadduct. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results.