Diiodoindium(III) Cation, InI2+, a Potent Yneophile. Generation and Application to Cationic Cyclization by Selective π-Activation of CC

被引：48

作者：

Surendra, Karavadhi ^{[1
]}

Corey, E. J. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 31期

关键词：

Cyclization - Chemical activation - Silver compounds - Carbon - Positive ions;

D O I：

10.1021/ja506502p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The removal of the iodide ion from indium triiodide by means of reactive Ag(I) salts leads to the formation of the highly reactive ligandless cation InI2+, which is unusual in having two vacant low-lying p-orbitals. This bivalent Lewis acidity leads to an especially high affinity for the two orthogonal pi-bonds of carbon-carbon triple bonds. Consequently, the double-coordinating InI2+ is an especially effective reagent for the selective activation of C C and the catalytic initiation of cationic cyclization processes. A number of such reactions are described to demonstrate synthetic utility.

引用

页码：10918 / 10920

页数：3

共 12 条

[1] Highly efficient access to strained bicyclic ketals via gold-catalyzed cycloisomerization of bis-homopropargylic diols [J].

Antoniotti, S ;

Genin, E ;

Michelet, V ;

Genêt, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (28) :9976-9977

[2]

Cristina N.-O., 2008, J AM CHEM SOC, V130, P269

[3] Chiral copper(II) complexes as Lewis acids for catalyzed cycloaddition, carbonyl addition, and conjugate addition reactions [J].

Evans, DA ;

Rovis, T ;

Johnson, JS .

PURE AND APPLIED CHEMISTRY, 1999, 71 (08) :1407-1415

[4] A novel chiral super-Lewis acidic catalyst for enantioselective synthesis [J].

Hayashi, Y ;

Rohde, JJ ;

Corey, EJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (23) :5502-5503

[5] Highly enantioselective palladium-catalyzed asymmetric Diels-Alder reactions with chiral phosphino-oxazoline ligands [J].

Hiroi, K ;

Watanabe, K .

TETRAHEDRON-ASYMMETRY, 2002, 13 (17) :1841-1843

[6] THE EFFECT OF ADDED SILVER-NITRATE ON THE PALLADIUM-CATALYZED ARYLATION OF ALLYLTRIMETHYLSILANES [J].

KARABELAS, K ;

WESTERLUND, C ;

HALLBERG, A .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (20) :3896-3900

[7] Chiral carbene approach to gold-catalyzed asymmetric cyclization of 1,6-enynes [J].

Matsumoto, Yasumasa ;

Selim, Khalid B. ;

Nakanishi, Hirotsugu ;

Yamada, Ken-ichi ;

Yamamoto, Yasutomo ;

Tomioka, Kiyoshi .

TETRAHEDRON LETTERS, 2010, 51 (02) :404-406

[8] Selective Formation of Six-Membered Oxa- and Carbocycles by the In(III)-Activated Ring Closure of Acetylenic Substrates [J].

Qiu, Wen-Wei ;

Surendra, Karavadhi ;

Yin, Liang ;

Corey, E. J. .

ORGANIC LETTERS, 2011, 13 (21) :5893-5895

[9] Gold(I)-Catalyzed Enantioselective Polycyclization Reactions [J].

Sethofer, Steven G. ;

Mayer, Timo ;

Toste, F. Dean .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (24) :8276-+

[10] A Powerful New Construction of Complex Chiral Polycycles by an Indium(III)-Catalyzed Cationic Cascade [J].

Surendra, Karavadhi ;

Qiu, Wenwei ;

Corey, E. J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (25) :9724-9726

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