Diels-Alder reactions of 1,1,3-triarylallyl cations: determination of the free energy of concert

被引：9

作者：

Fichtner, C ^{[1
]}

Mayr, H ^{[1
]}

机构：

[1] Univ Munich, Dept Chem, D-81377 Munich, Germany

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 2002年 / 08期

关键词：

D O I：

10.1039/b203555c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

1,1,3-Triarylallyl cations react with 1,3-dienes to give Diels-Alder products in low to moderate yields. The observed second-order rate constants agree with those calculated for the stepwise processes by the correlation log k(20 degreesC) = s(N + E) [eqn. (1)] indicating the absence of a significant free energy of concert. Eqn. (1) can, therefore, also be employed for the prediction of absolute rate constants of Diels-Alder reactions of allyl cations.

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页码：1441 / 1444

页数：4

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共 44 条

[1]

Alder K., 1955, EXPERIENTIA S, VII, P86

[2] Determination of the nucleophilicities of silyl and alkyl enol ethers [J].

Burfeindt, J ;

Patz, M ;

Müller, M ;

Mayr, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (15) :3629-3634

[3] The ionic Diels-Alder reaction of the allyl cation and butadiene: Theoretical investigation of the mechanism [J].

dePascualTeresa, B ;

Houk, KN .

TETRAHEDRON LETTERS, 1996, 37 (11) :1759-1762

[4] Determination of the nucleophilicities of N,N-bis(silyloxy)enamines [J].

Dilman, AD ;

Ioffe, SL ;

Mayr, H .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (09) :3196-3200

[5] FORBIDDEN REACTIONS - [2 + 2] CYCLOREVERSION OF RIGID CYCLOBUTANES [J].

DOERING, WV ;

ROTH, WR ;

BREUCKMANN, R ;

FIGGE, L ;

LENNARTZ, HW ;

FESSNER, WD ;

PRINZBACH, H .

CHEMISCHE BERICHTE-RECUEIL, 1988, 121 (01) :1-9

[6]

Fleming I., 1976, FRONTIER ORBITALS OR

[7] USE OF ALKYL SUBSTITUTION TO CONTROL RING SIZE IN THE INTRAMOLECULAR IONIC DIELS-ALDER REACTION [J].

GASSMAN, PG ;

GORMAN, DB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (23) :8623-8624

[8] CONTROL OF REGIOSPECIFICITY IN IONIC DIELS-ALDER REACTIONS - THE USE OF ALLYLIC ALCOHOLS AND ALLYLIC ETHERS AS PRECURSORS OF DIENOPHILIC ALLYL CATIONS [J].

GASSMAN, PG ;

SINGLETON, DA .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (15) :3075-3076

[9] STEPWISE MECHANISM FOR THE FORMATION OF 2-PI + 4-PI CYCLOADDUCTS IN THE IONIC DIELS-ALDER REACTION [J].

GASSMAN, PG ;

GORMAN, DB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (23) :8624-8626

[10] ACROLEIN ACETALS AS ALLYL CATION PRECURSORS IN THE IONIC DIELS-ALDER REACTION [J].

GASSMAN, PG ;

SINGLETON, DA ;

WILWERDING, JJ ;

CHAVAN, SP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (07) :2182-2184

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