Rhodium-Catalyzed [2+2+2] Cycloaddition Reactions of Linear Allene-Ene-Ynes to afford Fused Tricyclic Scaffolds: Insights into the Mechanism

被引：21

作者：

Cassu, Daniel ^{[1
,2
]}

Parella, Teodor ^{[3
]}

Sola, Miquel ^{[1
,2
]}

Pla-Quintana, Anna ^{[1
,2
]}

Roglans, Anna ^{[1
,2
]}

机构：

[1] Univ Girona, IQCC, Fac Ciencies, C Maria Aurelia Capmany 69, Girona 17003, Spain

[2] Univ Girona, Dept Quim, Fac Ciencies, C Maria Aurelia Capmany 69, Girona 17003, Spain

[3] Univ Autonoma Barcelona, Serv Ressonancia Magnet Nucl, E-08193 Barcelona, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 59期

关键词：

allenes; cycloaddition; density functional calculations; reaction mechanisms; rhodium; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; SYNTHETIC APPLICATIONS; CYCLIZATION REACTIONS; COMPLEXES; ALKYNES; CYCLOTRIMERIZATION; VINYLCYCLOPROPANES; REACTIVITY; CYCLOISOMERIZATIONS;

D O I：

10.1002/chem.201703194

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Allene-(E)-ene-yne N-tosyl-tethered substrates 3a-3h were efficiently prepared and their rhodium-catalyzed [2+2+2] cycloaddition reactions were evaluated. The cycloadditions are chemoselective as only the proximal double bond of the allene reacted to afford exocyclic double bonds in the fused-tricyclic scaffolds. The stereoselectivity depended on the catalytic system used. Reactivity between allene, alkene, and alkyne was studied for the first time by density functional theory calculations. This mechanistic study determines the order in which the unsaturated groups take part in the catalytic cycle.

引用

页码：14889 / 14899

页数：11

共 83 条

[1]

Albright T. A., 1985, ORBITAL INTERACTION

[2] Cyclization reactions of bis(allenes) for the synthesis of polycarbo(hetero) cycles [J].

Alcaide, Benito ;

Almendros, Pedro ;

Aragoncillo, Cristina .

CHEMICAL SOCIETY REVIEWS, 2014, 43 (09) :3106-3135

[3] Recent Advances in Stereoselective [2+2+2] Cycloadditions [J].

Amatore, Muriel ;

Aubert, Corinne .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2015, 2015 (02) :265-286

[4]

[Anonymous], 2008, ANGEW CHEM

[5]

Atkins P., 2006, PHYS CHEM

[6] Transition Metal Catalyzed Cycloisomerizations of 1,n-Allenynes and -Allenenes [J].

Aubert, Corinne ;

Fensterbank, Louis ;

Garcia, Pierre ;

Malacria, Max ;

Simonneau, Antoine .

CHEMICAL REVIEWS, 2011, 111 (03) :1954-1993

[7] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[8] Reaction of [TpRh(C2H4)2] with Dimethyl Acetylenedicarboxylate: Identification of Intermediates of the [2+2+2] Alkyne and Alkyne-Ethylene Cyclo(co)trimerizations [J].

Bottari, Giovanni ;

Santos, Laura L. ;

Posadas, Cristina M. ;

Campos, Jesus ;

Mereiter, Kurt ;

Paneque, Margarita .

CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (38) :13715-13723

[9] Recent Advances in Transition-Metal-Catalyzed [2+2+2]Cyclo(co)trimerization Reactions [J].

Broere, Daniel L. J. ;

Ruijter, Eelco .

SYNTHESIS-STUTTGART, 2012, 44 (17) :2639-2672

[10] Fused tetracycles with a benzene or cyclohexadiene core: [2+2+2] cycloadditions on macrocyclic systems [J].

Brun, Sandra ;

Garcia, Lidia ;

Gonzalez, Ivan ;

Torrent, Anna ;

Dachs, Anna ;

Pla-Quintana, Anna ;

Parella, Teodor ;

Roglans, Anna .

CHEMICAL COMMUNICATIONS, 2008, (36) :4339-4341

← 1 2 3 4 5 6 7 8 9 →