Calculations Predict That Heavy-Atom Tunneling Dominates Mobius Bond Shifting in [12]- and [16]Annulene

被引：6

作者：

Arbitman, Jessica K. ^{[1
]}

Michel, Cameron S. ^{[1
]}

Castro, Claire ^{[1
]}

Karney, William L. ^{[1
]}

机构：

[1] Univ San Francisco, Dept Chem, 2130 Fulton St, San Francisco, CA 94117 USA

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 21期

基金：

美国国家科学基金会;

关键词：

REARRANGEMENT; CYCLIZATION;

D O I：

10.1021/acs.orglett.9b03185

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The contribution of heavy-atom tunneling to reactions of [12]- and [16]annulene was probed using small-curvature tunneling rate calculations. At the CCSD(T)/cc-pVDZ//M06-2X/cc-pVDZ level, tunneling is predicted to account for more than 50% of the rate for Mobius bond shifting and ca. 35% of the rate for electrocyclization in [12]annulene, and over 80% of the rate for Mobius bond shifting in [16]annulene, at temperatures at which these reactions have been observed experimentally.

引用

页码：8587 / 8591

页数：5

共 37 条

[1]

[Anonymous], 2007, REV COMPUT CHEM

[2]

Bell R. P., 1980, TUNNEL EFFECT CHEM

[3] Reactions that involve tunneling by carbon and the role that calculations have played in their study [J].

Borden, Weston Thatcher .

WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2016, 6 (01) :20-46

[4] HEAVY-ATOM TUNNELING AS THE DOMINANT PATHWAY IN A SOLUTION-PHASE REACTION - BOND SHIFT IN ANTIAROMATIC ANNULENES [J].

CARPENTER, BK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (06) :1700-1701

[5] Mobius aromaticity in [12]annulene: Cis-trans isomerization via twist-coupled bond shifting [J].

Castro, C ;

Karney, WL ;

Valencia, MA ;

Vu, CMH ;

Pemberton, RP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (27) :9704-9705

[6] Heavy-Atom Tunneling Calculations in Thirteen Organic Reactions: Tunneling Contributions are Substantial, and Bell's Formula Closely Approximates Multidimensional Tunneling at ≥ 250K [J].

Doubleday, Charles ;

Armas, Randy ;

Walker, Dana ;

Cosgriff, Christopher V. ;

Greer, Edyta M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (42) :13099-13102

[7] The thermal retro[2+2+2]cycloaddition of cyclohexane activated by triscyclobutenannelation:: Concerted all-disrotatory versus stepwise conrotatory pathways to fused [12]Annulenes [J].

Eichberg, Michael J. ;

Houk, K. N. ;

Lehmann, Juerg ;

Leonard, Philip W. ;

Maerker, Anne ;

Norton, Joseph E. ;

Sawicka, Dorota ;

Vollhardt, K. Peter C. ;

Whitener, Glenn D. ;

Wolff, Stefan .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (36) :6894-6898

[8] Heavy-Atom Tunneling in the Ring Opening of a Strained Cyclopropene at Very Low Temperatures [J].

Ertelt, Melanie ;

Hrovat, David A. ;

Borden, Weston Thatcher ;

Sander, Wolfram .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (16) :4713-4720

[9]

Frisch M.J., 2016, GAUSSIAN 16

[10] Light- and Heavy-Atom Tunneling in Rearrangement Reactions of Cyclopropylcarbenes [J].

Gerbig, Dennis ;

Ley, David ;

Schreiner, Peter R. .

ORGANIC LETTERS, 2011, 13 (13) :3526-3529

← 1 2 3 4 →