A FAST CATALYTIC PROCESS OF TRANSFER OF A PHOSPHORUS ATOM: HOW FOLDING OF THE REAGENT IS RELATED TO ITS CATALYTIC ACTIVITY. A POSSIBLE CORRELATION WITH RNA BEHAVIOR

被引:2
作者
Baccolini, Graziano [1 ]
Micheletti, Gabriele [1 ]
机构
[1] Univ Bologna, ALMA MATER STUDIORUM, Dipartimento Chim Ind Toso Montanari, I-40136 Bologna, Italy
关键词
Phosphorus pentacoordinate; phosphorus trichloride; Grignard reagents; benzothiadiphosphole; RNA; ONE-POT SYNTHESIS; HEXACOORDINATE PHOSPHORUS; PENTACOORDINATE; HYDROLYSIS; INTERMEDIATE; MECHANISMS; CLEAVAGE; KINETICS;
D O I
10.1080/10426507.2014.883625
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A simple and very fast process of transfer of a phosphorus atom, performed by a simple molecule acting as catalyst in an almost infinite catalytic cycle is described. The catalyst donates a P atom to a mixture of two different Grignard reagents giving, in a very fast and in a highly selective manner, only one phosphorus-containing compound with an enormous rate enhancement with respect to the corresponding no-catalyzed reaction which gives a final cluttered mixture of many organophosphorus products. The focal factor to explain this highly selective process of P transport lies in the folded structure of the reagent with particular angles around the phosphorus atom which can facilitate the formation of cyclic trigonal bipyramidal pentacoordinated species and then its catalytic activity. In a similar manner, RNA can adopt, in a precise position, a particular three-dimensional structure that might facilitate the formation of pentacoordinated species leading to the catalytic function.
引用
收藏
页码:1254 / 1265
页数:12
相关论文
共 42 条
[1]  
[Anonymous], PHOSPHORUS 31 NMR SP
[2]   Efficient one-pot synthesis of secondary cyclic phosphanes with easy regeneration of the phosphorus-donor reagent used [J].
Baccolini, G ;
Boga, C ;
Galeotti, M .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (23) :3058-3060
[3]  
Baccolini G, 1997, HETEROATOM CHEM, V8, P551, DOI 10.1002/(SICI)1098-1071(1997)8:6<551::AID-HC15>3.0.CO
[4]  
2-Q
[5]  
Baccolini G, 2001, SYNTHESIS-STUTTGART, P1938
[6]   FACILE SYNTHESIS OF FUSED BENZO-1,2,3-THIADIPHOSPHOLES, A NEW HETEROCYCLIC SYSTEM [J].
BACCOLINI, G ;
MEZZINA, E ;
TODESCO, PE ;
FORESTI, E .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (04) :304-305
[7]   The Phosphoenolpyruvate Phosphorylation: A Self-Organized Mechanism with Implications to Understand the RNA Transformations [J].
Baccolini, Graziano ;
Boga, Carla ;
Micheletti, Gabriele .
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 2010, 185 (11) :2303-2315
[8]   General and efficient one-pot synthesis of tertiary phosphane-borane complexes containing different alkyl groups and in situ facile recycling of the phosphorus donor reagent [J].
Baccolini, Graziano ;
Boga, Carla ;
Mazzaeurati, Marzia .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2007, 2007 (27) :4529-4534
[9]   The Role Played by Phosphorus Hexacoordination in Driving the Stereochemical Outcome of a Phosphination Reaction [J].
Baccolini, Graziano ;
Micheletti, Gabriele ;
Boga, Carla .
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (17) :6812-6818
[10]   The First Flights of a Molecular Shuttle Transporting Elements: Easy One-pot Formation of Organic Cyclic Arsanes, Stibanes and Bismutanes [J].
Baccolini, Graziano ;
Boga, Carla ;
Mazzacurati, Marzia ;
Micheletti, Gabriele .
CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (03) :597-599