Active Metal Template Synthesis of [2]Catenanes

被引:113
作者
Goldup, Stephen M. [1 ]
Leigh, David A. [1 ]
Long, Tao [1 ]
McGonigal, Paul R. [1 ]
Symes, Mark D. [1 ]
Wu, Jhenyi [1 ]
机构
[1] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
关键词
MECHANICALLY INTERLOCKED MOLECULES; SELECTIVE CROSS-CATENATION; RING-CLOSING METATHESIS; ONE-POT SYNTHESIS; DIRECTED SYNTHESIS; EFFICIENT SYNTHESIS; THERMODYNAMIC CONTROL; ROTAXANE FORMATION; TRANSITION-METALS; CATENANES;
D O I
10.1021/ja9070317
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis of [2]catenanes by single macrocyclization and double macrocyclization strategies using Cu(l) ions to catalyze covalent bond formation while simultaneously acting as the template for the mechanically interlocked structure is reported. These "active metal template" strategies employ appropriately functionalized pyridine ether or bipyridine ligands and either the CuAAC "click" reaction of azides with terminal alkynes or the Cul(l)-mediated Cadiot-Chodkiewicz heterocoupling of an alkyne halide with a terminal alkyne. Using one macrocyclic and one acyclic building block, heterocircuit (the rings are constitutionally different) [2]catenanes are produced via the single macrocyclization route in up to 53% yield by optimizing the reaction conditions and relative stoichiometry of the starting materials. Alternatively, with the active template CuAAC reaction, a single acyclic unit can be used to form a homocircuit (two identical rings) [2]catenane in 46% yield through a one-pot, double macrocyclization, procedure. Remarkably, <7% of the corresponding noninterlocked macrocycle is isolated from this reaction, indicating the efficacy of Cu(l) as both a template for the catenane and a catalyst for covalent bond formation in the reaction.
引用
收藏
页码:15924 / 15929
页数:6
相关论文
共 146 条
[1]   A convenient route to unsymmetrical conjugated diynes [J].
Alami, M ;
Ferri, F .
TETRAHEDRON LETTERS, 1996, 37 (16) :2763-2766
[2]   Interlocked and intertwined structures and superstructures [J].
Amabilino, DB ;
Stoddart, JF .
CHEMICAL REVIEWS, 1995, 95 (08) :2725-2828
[3]  
[Anonymous], 2000, Templated organic synthesis
[4]   Clicked interlocked molecules [J].
Aprahamian, Ivan ;
Miljanic, Ognjen S. ;
Dichtel, William R. ;
Isoda, Kyosuke ;
Yasuda, Takuma ;
Kato, Takashi ;
Stoddart, J. Fraser .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2007, 80 (10) :1856-1869
[5]   Templated synthesis of interlocked molecules [J].
Aricó, F ;
Badjic, JD ;
Cantrill, SJ ;
Flood, AH ;
Leung, KCF ;
Liu, Y ;
Stoddart, JF .
TEMPLATES IN CHEMISTRY II, 2005, 249 :203-259
[6]   Template-directed synthesis of multiply mechanically interlocked molecules under thermodynamic control [J].
Aricó, F ;
Chang, T ;
Cantrill, SJ ;
Khan, SI ;
Stoddart, JF .
CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (16) :4655-4666
[7]   Synthesis of a [2]catenane around a Ru(diimine)32+ scaffold by ring-closing metathesis of olefins [J].
Arico, F ;
Mobian, P ;
Kern, JM ;
Sauvage, JP .
ORGANIC LETTERS, 2003, 5 (11) :1887-1890
[8]   Catalytic "click" rotaxanes:: A substoichiometric metal-template pathway to mechanically interlocked architectures [J].
Aucagne, V ;
Hänni, KD ;
Leigh, DA ;
Lusby, PJ ;
Walker, DB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (07) :2186-2187
[9]   Catalytic "Active-Metal" template synthesis of [2]rotaxanes, [3]rotaxanes, and molecular shuttles, and some observations on the mechanism of the Cu(I)-catalyzed azide-alkyne 1,3-cycloaddition [J].
Aucagne, Vincent ;
Berna, Jose ;
Crowley, James D. ;
Goldup, Stephen M. ;
Haenni, Kevin D. ;
Leigh, David A. ;
Lusby, Paul J. ;
Ronaldson, Vicki E. ;
Slawin, Alexandra M. Z. ;
Viterisi, Aurlien ;
Walker, D. Barney .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (39) :11950-11963
[10]   Self-assembly, binding, and dynamic properties of heterodimeric porphyrin macrocycles [J].
Ballester, P ;
Costa, A ;
Deyà, PM ;
Frontera, A ;
Gomila, RM ;
Oliva, AI ;
Sanders, JKM ;
Hunter, CA .
JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (17) :6616-6622