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 13 条

[1] Computational study of heavy-atom tunneling in the Mobius π-bond shifting in [12]- and [16]annulene
Michel, Cameron
Arbitman, Jessica
Castano, Ioannina
Karney, William
Castro, Claire
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2017, 253
[2] Heavy-atom tunneling in planar bond shifting of [16]annulene
Lampkin, Philip
Shezaf, Jonathan
Michel, Cameron
Castro, Claire
Karney, William
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2019, 257
[3] Tunneling by 16 Carbons: Planar Bond Shifting in [16]Annulene
Michel, Cameron S.
Lampkin, Philip P.
Shezaf, Jonathan Z.
Moll, Joseph F.
Castro, Claire
Karney, William L.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (13) : 5286 - 5293
[4] Computational study of heavy-atom tunneling in the Mobius pi-bond shifting in [4n]- and [4n+2]annulenes
Michel, Cameron
Arbitman, Jessica
Castro, Claire
Karney, William
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2018, 255
[5] Dynamic processes in [16]annulene: Mobius bond-shifting routes to configuration change
Pemberton, Ryan P.
McShane, Colleen M.
Castro, Claire
Karney, William L.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (51) : 16692 - 16700
[6] Mobius aromaticity in [12]annulene: Cis-trans isomerization via twist-coupled bond shifting
Castro, C
Karney, WL
Valencia, MA
Vu, CMH
Pemberton, RP
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (27) : 9704 - 9705
[7] Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon-Piperidine
Nandi, Ashim
Martin, Jan M. L.
JOURNAL OF PHYSICAL CHEMISTRY B, 2022, 126 (08): : 1799 - 1804
[8] HEAVY-ATOM TUNNELING AS THE DOMINANT PATHWAY IN A SOLUTION-PHASE REACTION - BOND SHIFT IN ANTIAROMATIC ANNULENES
CARPENTER, BK
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (06) : 1700 - 1701
[9] HEAVY-ATOM TUNNELING IN C-C BOND FORMATION FROM TRIPLET 1,3-BIRADICALS
DOUGHERTY, DA
JAIN, R
SPONSLER, MB
SNYDER, GJ
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1985, 190 (SEP): : 98 - PHS
[10] Heavy-Atom Tunneling Calculations in Thirteen Organic Reactions: Tunneling Contributions are Substantial, and Bell's Formula Closely Approximates Multidimensional Tunneling at ≥ 250K
Doubleday, Charles
Armas, Randy
Walker, Dana
Cosgriff, Christopher V.
Greer, Edyta M.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (42) : 13099 - 13102

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