Ring opening of 2-aza-3-borabicyclo[2.2.0]hex-5-ene, the Dewar form of 1,2-dihydro-1,2-azaborine: stepwise versus concerted mechanisms

被引:11
作者
Bettinger, Holger F. [1 ]
Hauler, Otto [1 ]
机构
[1] Univ Tubingen, Inst Organ Chem, D-72072 Tubingen, Germany
关键词
ab initio; azaborine; BN aromatics; Dewar isomer; reaction mechanism; PLESSET PERTURBATION-THEORY; GAUSSIAN-BASIS FUNCTIONS; VALENCE-BOND ISOMERS; ATOMIC BASIS-SETS; MOLECULAR CALCULATIONS; THERMAL REARRANGEMENT; COUPLED-CLUSTER; BENZENE; SPIN; THERMOCHEMISTRY;
D O I
10.3762/bjoc.9.86
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The ring opening of the Dewar form of 1,2-dihydro-1,2-azaborine, 2-aza-3-borabicyclo[2.2.0]hex-5-ene (3) is investigated by theoretical methods by using multiconfiguration SCF (CASSCF) and coupled cluster theory [CCSD(T)] with basis sets up to polarised quadruple-zeta quality. The title compound was previously reported to form photochemically in cryogenic noble gas matrices from 1,2-dihydro-1,2-azaborine (4). Four reaction paths for the thermal ring opening of 3 to 4 could be identified. These are the conventional disrotatory and conrotatory electrocyclic ring-opening pathways where the BN unit is only a bystander. Two more favourable paths are stepwise and involve 1,3-boron-carbon interactions. The lowest energy barrier for the isomerisation reaction, 22 kcal mol(-1), should be high enough for an experimental observation in solution. However, in solution the dimerisation of 3 is computed to have a very low barrier (3 kcal mol-1), and thus 3 is expected to be a short-lived reactive intermediate.
引用
收藏
页码:761 / 766
页数:6
相关论文
共 42 条
[1]  
Adam W., 1969, Int. J. Chem. Kinet, V1, P487, DOI DOI 10.1002/KIN.550010509
[2]  
[Anonymous], 2012, TURBOMOLE V6 4 2012
[3]   Is spin-component scaled second-order moller-plesset perturbation theory an appropriate method for the study of noncovalent interactions in molecules? [J].
Antony, Jens ;
Grimme, Stefan .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (22) :4862-4868
[4]   Scope and limitations of the SCS-MP2 method for stacking and hydrogen bonding interactions [J].
Bachorz, Rafa A. ;
Bischoff, Florian A. ;
Hoefener, Sebastian ;
Klopper, Wim ;
Ottiger, Philipp ;
Leist, Roman ;
Frey, Jann A. ;
Leutwyler, Samuel .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (19) :2758-2766
[5]   UNSYMMETRICAL SUBSTITUENT EFFECTS ON ANTIAROMATIC TRANSITION-STATE FOR REARRANGEMENT OF BICYCLO[2.2.0]HEXADIENE TI BENZENE [J].
BRESLOW, R ;
SCHMIDT, AH ;
NAPIERSK.J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (16) :5906-&
[6]   Photoisomerization of 1,2-Dihydro-1,2-Azaborine: A Matrix Isolation Study [J].
Brough, Sarah A. ;
Lamm, Ashley N. ;
Liu, Shih-Yuan ;
Bettinger, Holger F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (43) :10880-10883
[7]   ELECTROCYCLIC RING-OPENING OF 1ALPHA,4ALPHA BICYCLO[2.2.0]HEXA-2,5-DIENES AND 1ALPHA,4BETA-BICYCLO[2.2.0]HEXA-2,5-DIENES (CIS AND TRANS DEWAR BENZENES) - MNDO (MODIFIED NEGLECT OF DIATOMIC OVERLAP) SEMIEMPIRICAL MOLECULAR-ORBITAL CALCULATIONS [J].
DEWAR, MJS ;
FORD, GP ;
RZEPA, HS .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (20) :728-730