Uncharacteristic thione behavior in a Huisgen cycloaddition reaction: a kinetic and theoretical study

被引：7

作者：

Butler, Richard N. ^{[1
]}

Coyne, Anthony G.

McArdle, Patrick

Sibley, Lisa M.

Burke, Luke A.

机构：

[1] Natl Univ Ireland Univ Coll Galway, Dept Chem, Galway, Ireland

[2] Rutgers State Univ, Dept Chem, Camden, NJ 08102 USA

来源：

TETRAHEDRON LETTERS | 2007年 / 48卷 / 38期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/j.tetlet.2007.07.138

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In the reaction of phthalazinium-2-dicyanomethanide with adamantanethione the rare ring system [1,3]thiazolo[2,3a]phthalazine was obtained. An X-ray crystal structure of the product shows regioselectivity with the thione carbon bonded to the dicyanomethanide terminus of the 1,3-dipole. UV kinetic measurements and DFT calculations showed that the rate of cycloaddition of adamantanethione was significantly slower than that of DMAD and no super-dipolarophile character was exhibited. This arose from exceptional lowering of the HOMO energy of the 1,3-dipole by the cyano substituents. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：6684 / 6687

页数：4

共 30 条

[1]

[Anonymous], [No title captured]

[2] A NEW ACCESS TO PHOSPHAINDOLIZINES BY [3+2] CYCLOADDITION OF AZOMETHINE YLIDES ONTO PHOSPHAALKYNES [J].

BERGSTRASSER, U ;

HOFFMANN, A ;

REGITZ, M .

TETRAHEDRON LETTERS, 1992, 33 (08) :1049-1052

[3] The influence of water on the rates of 1,3-dipolar cycloaddition reactions: Trigger points for exponential rate increases in water-organic solvent mixtures. Water-super versus water-normal dipolarophiles [J].

Butler, RN ;

Cunningham, WJ ;

Coyne, AG ;

Burke, LA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (38) :11923-11929

[4] Kinetic and synthetic influences of water and solvent-free conditions on 1,3-dipolar cycloaddition reactions: the phthalazinium and pyridazinium dicyanomethanide 1,3-dipoles: surprisingly successful synthetic methods [J].

Butler, RN ;

Coyne, AG ;

Cunningham, WJ ;

Burke, LA .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2002, (11) :1807-1815

[5] The kinetic profile of phthalazinium-2-dicyanomethanide 1,3-dipole with 2π-dipolarophiles:: U-shaped dipolarophilic activity and classic type II dipole behaviour.: Reaction rates and DFT calculations [J].

Butler, RN ;

Coyne, AG ;

Burke, LA .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2001, (09) :1781-1784

[6] The reactions of phthalazinium-2-(unsubstituted)methanide and aryl(3-phenylprop-2-en-1-ylidene)ammoniomethanide 1,3-dipoles with some thioester and thioketone C=S dipolarophiles. Regio- and stereochemistry: substituted thiazolo-[4,3-a]- and -[2,3-a]-phthalazines and 2- and 4-styryl substituted tetrahydrothiazoles [J].

Butler, RN ;

Farrell, DM ;

McArdle, P ;

Cunningham, D .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1998, (05) :869-873

[7] Regioselectivity and endo/exo selectivity in the cycloadditions of the phthalazinium dicyanomethanide 1,3-dipole with unsymmetrical alkene and alkyne dipolarophiles.: Unexpected reversals of regiochemistry:: a combined experimental and DFT theoretical study [J].

Butler, RN ;

Coyne, AG ;

McArdle, P ;

Cunningham, D ;

Burke, LA .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2001, (12) :1391-1397

[8] 1,3-Thiazolidine derivatives from regioselective [2+3]-cycloadditions of azomethine ylides with thioketones [J].

Domagala, M ;

Linden, A ;

Olszak, TA ;

Mloston, G ;

Heimgartner, H .

ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY, 2003, 59 (05) :O250-O253

[9] New thione chemistry [J].

Fisera, L ;

Huisgen, R ;

Kalwinsch, I ;

Langhals, E ;

Li, XY ;

Mloston, G ;

Polborn, K ;

Rapp, J ;

Sicking, W ;

Sustmann, R .

PURE AND APPLIED CHEMISTRY, 1996, 68 (04) :789-798

[10] CHEMISTRY OF 2-SUBSTITUTED ADAMANTANES .1. ADAMANTANETHIONE, ITS DIMER AND TRIMER [J].

GREIDANUS, JW .

CANADIAN JOURNAL OF CHEMISTRY-BACK YEAR, 1970, 48 (22) :3530-+

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