Designing a catalytic synthesis of 4-methylcoumarin from ortho-iodophenyl 3-butenoate: Ring closure and isomerization control

Catellani, Marta; Chiusoli, Gian Paolo; Marzolini, Giovanna; Rossi, E.

doi:10.1016/s0022-328x(96)06489-3

Cited by 19 publications

(6 citation statements)

References 40 publications

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“…4-Methylcoumarin was synthesized in quantitative yield by the cyclization of 2-(iodophenyl)butenoate in the presence of catalytic amounts of Pd(0) [29].…”

Section: Catalytic Methods Of Constructing the Coumarin Skeletonmentioning

confidence: 99%

Catalytic methods of creation and functionalization of the coumarin skeleton

Fedorov

Nyuchev

Beletskaya

2012

Chem Heterocycl Comp

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“…4-Methylcoumarin was synthesized in quantitative yield by the cyclization of 2-(iodophenyl)butenoate in the presence of catalytic amounts of Pd(0) [29].…”

Section: Catalytic Methods Of Constructing the Coumarin Skeletonmentioning

confidence: 99%

Catalytic methods of creation and functionalization of the coumarin skeleton

Fedorov

Nyuchev

Beletskaya

2012

Chem Heterocycl Comp

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“…In contrast to the acidic conditions usually used in the Pechmann reaction, a base is employed as a catalyst of the reaction [171]. An interesting palladium-catalysed synthesis of 3-and/or 4-disubstituted coumarins have also been described [168,169]. In this reaction, phenylacetylene can act as a promotor for the formation of 4-methylcoumarin, or as a reagent for the synthesis of 4-phenylethinyl-3-(1-alkenyl)coumarins [169].…”

Section: Miscellaneousmentioning

confidence: 99%

Simple Coumarins and Analogues in Medicinal Chemistry: Occurrence, Synthesis and Biological Activity

Borges¹,

Roleira²,

Milhazes³

et al. 2005

CMC

883

458

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Coumarins, also known as benzopyrones, are present in remarkable amounts in plants, although their presence has also been detected in microorganisms and animal sources. The structural diversity found in this family of compounds led to the division into different categories, from simple coumarins to many other kinds of policyclic coumarins, such as furocoumarins and pyranocoumarins. Simple coumarins and analogues are a large class of compounds that have attracted their interest for a long time due to their biological activities: they have shown to be useful as antitumoural, anti-HIV agents and as CNS-active compounds. Furthermore, they have been reported to have multiple biological activities (anticoagulant, anti-inflammatory), although all these properties have not been evaluated systematically. In addition, their enzyme inhibition properties, antimicrobial and antioxidant activities are other foremost topics of this field of research. The present work is to survey the information published or abstracted from 1990 till 2003, which is mainly related to the occurrence, synthesis and biological importance of simple coumarins and some analogues, such as biscoumarins and triscoumarins. Data are also highlighted, concerning the development of new synthetic strategies that could help in drug design and in the work on SAR or QSAR.

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“…We have shown that (2-X-aryl)palladium complexes have interesting properties when X is a reactive substituent such as CHO, C(O)Me, C(O)NHR, NH 2 , NO 2 , CN, and CHCH 2 . − In this paper we report the synthesis of complexes with X = OH, OC(O)Me, and OC(O)CHCH 2 . These complexes seem to play an important role in some palladium-catalyzed processes, e.g., in the formation of o -alkynylphenols, which are intermediates in the formation of benzofurans. − Similarly, ortho-palladated O-substituted phenol derivatives may be catalytic intermediates in intramolecular cyclizations to give 4-methylcoumarin, , 1,3-benzoxazepin-2-ones, or benzopyrans . However, as far as we are aware, ortho-palladated phenol or phenol ester derivatives have not yet been isolated; in this work, we report on the synthesis of these types of complexes and on their reactivity with carbon monoxide and isonitriles.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles

et al. 2001

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The reaction of 2-ROC6H4I with [Pd2(dba)3]·dba (“Pd(dba)2”; dba = dibenzylideneacetone) in the presence of the appropriate ligand results in the formation of the arylpalladium complexes trans-[Pd(C6H4OR-2)I(PPh3)2] (R = H (1a), C(O)Me (1b), C(O)CHCH2 (1c)) and [Pd(C6H4OR-2)I(bpy)] (bpy = 2,2‘-bipyridine; R = H (2a), C(O)Me (2b)). Complexes 1b and 1c react with bpy in the presence of Tl(OTf) (OTf = OSO2CF3) to give the cationic species [Pd(C6H4OR-2)(bpy)(PPh3)]OTf (R = C(O)Me (3b), C(O)CHCH2 (3c)). Complex 1a reacts with carbon monoxide, yielding the insertion complex trans-[Pd{C(O)C6H4OH-2}I(PPh3)2] (4a). Complexes 2a and 2b can also be carbonylated to give [Pd{C(O)C6H4OR-2}I(bpy)] (R = H (5a), C(O)Me (5b)). Complex 4a reacts with bpy and Tl(OTf), giving [Pd{C(O)C6H4OH-2}(bpy)(PPh3)]OTf (6a). The reaction of 2-ROC6H4I with Pd(dba)2 and isonitriles R‘NC gives rise to the complexes trans-[Pd{C(NR‘)C6H4OR-2}I(CNR‘)2] (R = H, R‘ = Xy = 2,6-dimethylphenyl) (7a), R‘ = t Bu (7a*); R = C(O)Me, R‘ = Xy (7b), R‘ = t Bu (7b*)). Complexes 7a and 7b* can also be prepared by ligand displacement from 2a and 2b and XyNC and t BuNC, respectively. Complexes 2a and 2b react with R‘NC (1:1) to give [Pd{C(NR‘)C6H4OR-2}I(bpy)] (R = H, R‘ = Xy (8a), R‘ = t Bu (8 a *); R = C(O)Me, R‘ = Xy (8b)). Complex 7a reacts with bpy in the presence of Tl(OTf), yielding [Pd{C(NR‘)C6H4OH-2}(CNR‘)(bpy)]OTf (9a). Reaction of 5a with R‘NC gives trans-[Pd{C(O)C6H4OH-2}I(CNR‘)2] (R‘ = Xy (10a), t Bu (10 a *)), which, in turn, react with further R‘NC in the presence of Tl(OTf) to give [Pd{C(O)C6H4OH-2}(CNR‘)3]OTf (R‘ = Xy (11a), t Bu (11 a *)). Finally, the reaction of 7a with Pd(OAc)2 results in the tetrameric [Pd{κ 2(C,O)- μ 2(O)-C(NXy)C6H4O-2}(CNXy)]4 (12) and trans-[PdI2(CNXy)2]. Most of the reported aroyl (4−6, 10, 11) and iminoaroyl (7−9, 12) derivatives are new types of palladium complexes. The crystal structures of complexes 5a, 7a, 7b, 8b, 9a, and 12 have been determined by X-ray diffraction methods. The following scale of trans influence has been established: bpy < I < C(NXy)C6H4OC(O)Me-2 ≈ C(O)C6H4OH-2 < C(NXy)C6H4OH-2.

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Designing a catalytic synthesis of 4-methylcoumarin from ortho-iodophenyl 3-butenoate: Ring closure and isomerization control

Cited by 19 publications

References 40 publications

Catalytic methods of creation and functionalization of the coumarin skeleton

Catalytic methods of creation and functionalization of the coumarin skeleton

Simple Coumarins and Analogues in Medicinal Chemistry: Occurrence, Synthesis and Biological Activity

Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles

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