共 23 条
Differential Effects of Nitrogen Substitution in 5-and 6-Membered Aromatic Motifs
被引:0
作者:

Levandowski, Brian J.
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, MA

Abularrage, Nile S.
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, MA

Raines, Ronald T.
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, MA
机构:
[1] Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, MA
关键词:
aromaticity;
cycloaddition;
density functional calculations;
kinetics;
D O I:
10.1002/chem.202001542
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The replacement of carbon with nitrogen can affect the aromaticity of organic rings. Nucleus-independent chemical shift (NICS) calculations at the center of the aromatic π-systems reveal that incorporating nitrogen into 5-membered heteroaromatic dienes has only a small influence on aromaticity. In contrast, each nitrogen incorporated into benzene results in a sequential and substantial loss of aromaticity. The contrasting effects of nitrogen substitution in 5-membered dienes and benzene are reflected in their Diels-Alder reactivities as dienes. 1,2-Diazine experiences a 1011 -fold increase in reactivity upon nitrogen substitution at the 4- and 5-positions, whereas a 5-membered heteroaromatic diene, furan, experiences a comparatively incidental 102 -fold increase in reactivity upon nitrogen substitution at the 3- and 4-positions. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
引用
收藏
页码:8833 / 8833
页数:1
相关论文
共 23 条
[1]
THE REACTIVITY OF NITROGEN HETEROCYCLICS WITH RESPECT TO CYCLOOCTYNE AS THE DIENOPHILE
[J].
BALCAR, J
;
CHRISAM, G
;
HUBER, FX
;
SAUER, J
.
TETRAHEDRON LETTERS,
1983, 24 (14)
:1481-1484

BALCAR, J
论文数: 0 引用数: 0
h-index: 0
机构:
UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER

CHRISAM, G
论文数: 0 引用数: 0
h-index: 0
机构:
UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER

HUBER, FX
论文数: 0 引用数: 0
h-index: 0
机构:
UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER

SAUER, J
论文数: 0 引用数: 0
h-index: 0
机构:
UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER UNIV REGENSBURG,INST ORGAN CHEM,D-8400 REGENSBURG,FED REP GER
[2]
Heteroaromaticity .10. The direct calculation of resonance energies of azines and azoles from molecular dimensions
[J].
Bird, CW
.
TETRAHEDRON,
1997, 53 (38)
:13111-13118

Bird, CW
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, King's College London, London W8 7AH, Campden Hill
[3]
Tetrazine ligation: Fast bioconjugation based on inverse-electron-demand Diels-Alder reactivity
[J].
Blackman, Melissa L.
;
Royzen, Maksim
;
Fox, Joseph M.
.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
2008, 130 (41)
:13518-+

Blackman, Melissa L.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA

Royzen, Maksim
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA

Fox, Joseph M.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA
[4]
DIELS-ALDER REACTIONS OF HETEROCYCLIC AZADIENES - SCOPE AND APPLICATIONS
[J].
BOGER, DL
.
CHEMICAL REVIEWS,
1986, 86 (05)
:781-793

BOGER, DL
论文数: 0 引用数: 0
h-index: 0
[5]
Nucleus-independent chemical shifts (NICS) as an aromaticity criterion
[J].
Chen, ZF
;
Wannere, CS
;
Corminboeuf, C
;
Puchta, R
;
Schleyer, PV
.
CHEMICAL REVIEWS,
2005, 105 (10)
:3842-3888

Chen, ZF
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA

Wannere, CS
论文数: 0 引用数: 0
h-index: 0
机构: Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA

Corminboeuf, C
论文数: 0 引用数: 0
h-index: 0
机构: Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA

Puchta, R
论文数: 0 引用数: 0
h-index: 0
机构: Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA

Schleyer, PV
论文数: 0 引用数: 0
h-index: 0
机构: Univ Georgia, Computat Chem Annex, Athens, GA 30602 USA
[6]
Substituent Effects on "Hyperconjugative" Aromaticity and Antiaromaticity in Planar Cyclopolyenes
[J].
Fernandez, Israel
;
Wu, Judy I.
;
Schleyer, Paul von Rague
.
ORGANIC LETTERS,
2013, 15 (12)
:2990-2993

Fernandez, Israel
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Complutense Madrid, Fac Ciencias Quim, Dept Quim Organ 1, E-28040 Madrid, Spain Univ Complutense Madrid, Fac Ciencias Quim, Dept Quim Organ 1, E-28040 Madrid, Spain

Wu, Judy I.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Georgia, Dept Chem, Ctr Computat Chem, Athens, GA 30602 USA Univ Complutense Madrid, Fac Ciencias Quim, Dept Quim Organ 1, E-28040 Madrid, Spain

Schleyer, Paul von Rague
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Georgia, Dept Chem, Ctr Computat Chem, Athens, GA 30602 USA Univ Complutense Madrid, Fac Ciencias Quim, Dept Quim Organ 1, E-28040 Madrid, Spain
[7]
1,2,4-Triazines Are Versatile Bioorthogonal Reagents
[J].
Kamber, David N.
;
Liang, Yong
;
Blizzard, Robert J.
;
Liu, Fang
;
Mehl, Ryan A.
;
Houk, K. N.
;
Prescher, Jennifer A.
.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
2015, 137 (26)
:8388-8391

Kamber, David N.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Liang, Yong
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Blizzard, Robert J.
论文数: 0 引用数: 0
h-index: 0
机构:
Oregon State Univ, Dept Biochem & Biophys, Corvallis, OR 97331 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Liu, Fang
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Mehl, Ryan A.
论文数: 0 引用数: 0
h-index: 0
机构:
Oregon State Univ, Dept Biochem & Biophys, Corvallis, OR 97331 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Houk, K. N.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
Univ Calif Los Angeles, Dept Chem & Biomol Engn, Los Angeles, CA 90095 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

Prescher, Jennifer A.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
Univ Calif Irvine, Dept Mol Biol & Biochem, Irvine, CA 92697 USA
Univ Calif Irvine, Dept Pharmaceut Sci, Irvine, CA 92697 USA Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
[8]
Separation of the energetic and geometric contributions to the aromaticity .4. A general model for the pi-electron systems.
[J].
Krygowski, TM
;
Cyranski, M
.
TETRAHEDRON,
1996, 52 (30)
:10255-10264

Krygowski, TM
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, University of Warsaw, 02-093 Warsaw

Cyranski, M
论文数: 0 引用数: 0
h-index: 0
机构: Department of Chemistry, University of Warsaw, 02-093 Warsaw
[9]
Hyperconjugative Antiaromaticity Activates 4H-Pyrazoles as Inverse-Electron-Demand Diels-Alder Dienes
[J].
Levandowski, Brian J.
;
Abularrage, Nile S.
;
Houk, K. N.
;
Raines, Ronald T.
.
ORGANIC LETTERS,
2019, 21 (20)
:8492-8495

Levandowski, Brian J.
论文数: 0 引用数: 0
h-index: 0
机构:
MIT, Dept Chem, Cambridge, MA 02139 USA
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA MIT, Dept Chem, Cambridge, MA 02139 USA

Abularrage, Nile S.
论文数: 0 引用数: 0
h-index: 0
机构:
MIT, Dept Chem, Cambridge, MA 02139 USA MIT, Dept Chem, Cambridge, MA 02139 USA

Houk, K. N.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA MIT, Dept Chem, Cambridge, MA 02139 USA

Raines, Ronald T.
论文数: 0 引用数: 0
h-index: 0
机构:
MIT, Dept Chem, Cambridge, MA 02139 USA MIT, Dept Chem, Cambridge, MA 02139 USA
[10]
Hyperconjugative Aromaticity and Antiaromaticity Control the Reactivities and π-Facial Stereoselectivities of 5-Substituted Cyclopentadiene Diels-Alder Cycloadditions
[J].
Levandowski, Brian J.
;
Zou, Lufeng
;
Houk, K. N.
.
JOURNAL OF ORGANIC CHEMISTRY,
2018, 83 (23)
:14658-14666

Levandowski, Brian J.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

Zou, Lufeng
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

Houk, K. N.
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA