Finding the right path: Baldwin "Rules for Ring Closure" and stereoelectronic control of cyclizations

被引:139
作者
Alabugin, Igor V. [1 ]
Gilmore, Kerry [1 ]
机构
[1] Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA
基金
美国国家科学基金会;
关键词
INTRAMOLECULAR ORGANOMETAL-ACETYLENE; RADICAL TRANSLOCATION REACTIONS; STEREOCHEMISTRY; ALKYLLITHIUMS; CATALYSIS; ALKYNES;
D O I
10.1039/c3cc43872d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Truly important scientific breakthroughs often come from catching the glimpses of order in chaos and distilling a large body of disjointed data into a clear set of simple concepts. Even more impressive is when the new conceptual framework is created with some of the keystones still missing. Such bold predictions, i.e. Mendeleev's eka-silicon, challenge and inspire, serving as powerful catalysts for scientific growth. The rules for ring closure formulated by Sir Jack Baldwin in 1976 constitute one of such bold intellectual advances. Baldwin developed a classification system that brought order to the chaos of possible cyclization patterns and suggested a set of rules to define the favourable modes of ring closure. Where sufficient data was lacking, particularly for the cyclizations of alkynes, Baldwin made testable predictions that challenged theoretical and experimental chemists. These guidelines have become the common starting point in the design of new cyclization reactions and catalyzed the development of modern stereoelectronic concepts.
引用
收藏
页码:11246 / 11250
页数:5
相关论文
共 40 条
[1]   In search of efficient 5-endo-dig cyclization of a carbon-centered radical: 40 years from a prediction to another success for the Baldwin rules [J].
Alabugin, Igor V. ;
Timokhin, Vitaliy I. ;
Abrams, Jason N. ;
Manoharan, Mariappan ;
Abrams, Rachel ;
Ghiviriga, Ion .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (33) :10984-10995
[2]   Radical cascade transformations of tris(o-aryleneethynylenes) into substituted benzo[a]indeno[2,1-c]fluorenes [J].
Alabugin, Igor V. ;
Gilmore, Kerry ;
Patil, Satish ;
Manoharan, Mariappan ;
Kovalenko, Serguei V. ;
Clark, Ronald J. ;
Ghiviriga, Ion .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (34) :11535-11545
[3]   Rules for Anionic and Radical Ring Closure of Alkynes [J].
Alabugin, Igor V. ;
Gilmore, Kerry ;
Manoharan, Mariappan .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (32) :12608-12623
[4]   Thermodynamic and strain effects in the competition between 5-exo-dig and 6-endo-dig cyclizations of vinyl and aryl radicals [J].
Alabugin, IV ;
Manoharan, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (36) :12583-12594
[5]   5-endo-dig radical cyclizations: "The poor cousins" of the radical cyclizations family [J].
Alabugin, IV ;
Manoharan, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (26) :9534-9545
[6]   Intramolecular radical hydrosilylation -: the first radical 5-endo-dig cyclisation [J].
Amrein, S ;
Studer, A .
CHEMICAL COMMUNICATIONS, 2002, (15) :1592-1593
[7]   Generation and cyclization of a benzyne-tethered alkyllithium: Preparation of 4-substituted indans [J].
Bailey, WF ;
Longstaff, SC .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (03) :432-433
[8]   KINETICS OF THE CYCLIZATION OF 5-HEXYN-1-YLLITHIUMS [J].
BAILEY, WF ;
OVASKA, TV .
ORGANOMETALLICS, 1990, 9 (05) :1694-1695
[9]   INTRAMOLECULAR ADDITION OF ALKYLLITHIUMS TO ACETYLENES - REGIOSPECIFIC 4-EXO-DIG, 5-EXO-DIG, AND 6-EXO-DIG CYCLIZATIONS [J].
BAILEY, WF ;
OVASKA, TV .
TETRAHEDRON LETTERS, 1990, 31 (05) :627-630
[10]   FACILE PREPARATION OF ALKENYLIDENECYCLOALKANES BY CYCLIZATION OF ACETYLENIC ALKYLLITHIUMS BEARING A PROPARGYLIC LEAVING GROUP [J].
BAILEY, WF ;
ASPRIS, PH .
JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (03) :754-757