1,7-cyclization of 1-diazo-2,4-pentadiene and its heteroanalogues: DFT study / Subbotina Julia O.,Bakulev V. A.,Herges R.,Fabian W. M. F. // INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY. - 2006. - V. 106, l. 10. - P. 2229-2235.

ISSN/EISSN:

0020-7608 / нет данных

Type:

Article; Proceedings Paper

Abstract:

1,7-Dipolar cyclizations of 1-diazo-2,4-pentadiene 1a and its heteroanalogues 1b,c and 4c were studied using density functional theory (DFT). Although the heteroanalogue 1c has an appropriate electronic structure to allow for pseudopericyclic cyclization, natural bond order (NBO) analysis has provided evidence for the electrocyclic ring closure. Magnetic criteria (anisotropy of the induced current density {[}ACID], nucleus-independent chemical shifts {[}NICS]) confirmed the pericyclic character of the located transition states 2a,c and 5c. The activation barriers for the cyclization of 1-diazo-2,4-pentadiene la and its aza analogues 1c, 4c are 3.3, 8.2, and 12.3 kcal/mol at the B3LYP/6-31G(d) level, respectively. The higher barrier of the 1c -> 3c and 4c -> 3c reactions compared with 1a -> 3a is in line with the Hammond postulate. The out-of-plane distorted geometry of the cyclic product is an additional factor arguing against a pseudopericyclic mechanism. (c) 2006 Wiley Periodicals, Inc.

Author keywords:

pericyclic reactions; dipolar cyclization; DFT; ACID; NICS; NBO eb AROMATIC TRANSITION-STATES; DENSITY-FUNCTIONAL THEORY; AB-INITIO; PSEUDOPERICYCLIC REACTIONS; PERICYCLIC-REACTIONS; MAGNETIC-PROPERTIES; CYCLIZATION; MOLECULES; DELOCALIZATION; REARRANGEMENT

DOI:

10.1002/qua.20947

Web of Science ID:

ISI:000238243700009

Соавторы в МНС:

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Другие поля

Поле	Значение
Month	AUG 15
Note	9th Annual Meeting of the V-A-Fock-School on Quantum and Computational Chemistry, Novgorod, RUSSIA, MAY 10-15, 2005
Organization	V A Fock Sch
Publisher	JOHN WILEY \& SONS INC
Address	111 RIVER ST, HOBOKEN, NJ 07030 USA
Language	English
Keywords-Plus	AROMATIC TRANSITION-STATES; DENSITY-FUNCTIONAL THEORY; AB-INITIO; PSEUDOPERICYCLIC REACTIONS; PERICYCLIC-REACTIONS; MAGNETIC-PROPERTIES; CYCLIZATION; MOLECULES; DELOCALIZATION; REARRANGEMENT
Research-Areas	Chemistry; Mathematics; Physics
Web-of-Science-Categories	Chemistry, Physical; Mathematics, Interdisciplinary Applications; Physics, Atomic, Molecular \& Chemical
Author-Email	julia\_subbotina@mail.ru
ResearcherID-Numbers	Subbotina, Julia/L-7131-2016
ORCID-Numbers	Subbotina, Julia/0000-0002-2227-0787
Number-of-Cited-References	48
Usage-Count-Last-180-days	2
Usage-Count-Since-2013	3
Journal-ISO	Int. J. Quantum Chem.
Doc-Delivery-Number	052OT