Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic Units into Isoquinoline-1-thiones or Quinolin-4-ones as a Function of the Acetalic Ring Size

被引:5
作者
Alajarin, Mateo [1 ]
Marin-Luna, Marta [2 ]
Sanchez-Andrada, Pilar [1 ]
Vidal, Angel [1 ]
机构
[1] Univ Murcia, Fac Chem, Dept Organ Chem, Reg Campus Int Excellence Campus Mare Nostrum, E-30100 Murcia, Spain
[2] Univ Vigo, Dept Quim Organ, Campus Lagoas Marcosende, Vigo 36310, Spain
关键词
HYDROGEN-ATOM TRANSFER; BOND FUNCTIONALIZATION; THERMAL CYCLIZATION; TANDEM PROCESSES; ORTHO POSITION; CASCADE; PHENYLALLENES; CONSTRUCTION; DERIVATIVES; CHEMISTRY;
D O I
10.1021/acs.joc.9b01014
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
C-Alkoxycarbonyl-C-phenyl-N-aryl ketenimines bearing 1,3-dithiolan-2-yl or 1,3-dithian-2-yl substituents at ortho position of the C-phenyl ring, respectively, transform into isoquino-line-1-thiones and quinolin-4-ones under thermal treatment in toluene solution. The formation of isoquinolinethiones involves a rare degradation of the 1,3-dithiolane ring, whereas, in contrast, the 1,3-dithiane ring remains intact during the reaction course leading to quinolin-4-ones. Computational density functional theory results support that the kinetically favorable mechanism for the formation of isoquinoline-l-thiones proceeds through a [1,5]-hydride shift/6 pi-electrocyclization cascade, followed by a thiirane extrusion process. Alternative mechanistic paths showing interesting electronic reorganization processes have been also scrutinized but resulted not competitive on energetic grounds.
引用
收藏
页码:8140 / 8150
页数:11
相关论文
共 51 条
[1]   Thermal cyclization of N-[2-(2-propenyl)-1-naphthyl] ketenimines:: intramolecular Diels-Alder reaction versus [1,5] hydrogen migration.: Synthesis of dibenz[b,h]acridines and benzo[h]quinolines [J].
Alajarín, M ;
Vidal, A ;
Ortín, MM .
TETRAHEDRON, 2005, 61 (32) :7613-7621
[2]   Hydricity-promoted [1,5]-H shifts in acetalic ketenimines and carbodiimides [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Ortin, Maria-Mar ;
Sanchez-Andrada, Pilar ;
Vidal, Angel .
ORGANIC LETTERS, 2006, 8 (24) :5645-5648
[3]   Tandem processes promoted by a hydrogen shift in 6-aryl-fulvenes bearing acetalic units at ortho position: a combined experimental and computational study [J].
Alajarin, Mateo ;
Marin-Luna, Marta ;
Sanchez-Andrada, Pilar ;
Vidal, Angel .
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2016, 12 :260-270
[4]   Thermal Cyclization of Phenylallenes That Contain ortho-1,3-Dioxolan-2-yl Groups: New Cascade Reactions Initiated by 1,5-Hydride Shifts of Acetalic H Atoms [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Marin-Luna, Marta ;
Sanchez-Andrada, Pilar ;
Vidal, Angel .
CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (47) :16093-16103
[5]   1,5-(H, RO, RS) shift/6π-electrocyclic ring closure tandem processes on N-[(α-heterosubstituted)-2-tolyl]-ketenimines: a case study of relative migratory aptitudes and activating effects [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Orenes, Raul-Angel ;
Ortin, Maria-Mar ;
Vidal, Angel .
ORGANIC & BIOMOLECULAR CHEMISTRY, 2012, 10 (48) :9523-9537
[6]   Recent Highlights in Ketenimine Chemistry [J].
Alajarin, Mateo ;
Marin-Luna, Marta ;
Vidal, Angel .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (29) :5637-5653
[7]   Tandem [1,5]-H shift/6π-electrocyclizations of ketenimines bearing 1,3-oxathiane units. Computational assessment of the experimental diastereoselection [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Marin-Luna, Marta ;
Sanchez-Andrada, Pilar ;
Vidal, Angel ;
Orenes, Raul-Angel .
TETRAHEDRON, 2012, 68 (24) :4672-4681
[8]   Tandem 1,5-Hydride Shift/6p Electrocyclization of Ketenimines and Carbodiimides Substituted with Cyclic Acetal and Dithioacetal Functions: Experiments and Computations [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Ortin, Maria-Mar ;
Sanchez-Andrada, Pilar ;
Vidal, Angel .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (10) :1896-1913
[9]   Functionalization of Acetalic C(sp3)-H Bonds by Scandium(III) Triflate-Catalyzed Intramolecular Redox Reactions: Tandem 1,4-Hydride Transfer/1,5-Cyclization Processes Leading to Protected 1-Indanones [J].
Alajarin, Mateo ;
Marin-Luna, Marta ;
Vidal, Angel .
ADVANCED SYNTHESIS & CATALYSIS, 2011, 353 (04) :557-562
[10]   Tandem 1,5-Hydride Shift/1,5-S,N-Cyclization with Ethylene Extrusion of 1,3-Oxathiolane-Substituted Ketenimines and Carbodiimides. An Experimental and Computational Study [J].
Alajarin, Mateo ;
Bonillo, Baltasar ;
Sanchez-Andrada, Pilar ;
Vidal, Angel .
JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (11) :3737-3750