Arylation of allylphosphonates and application to the preparation of phosphonomethyl-coumarin, -quinolinone and -benzoxepinone skeletons Abderrahmen Abdelli a,b , Anne Gaucher a , Mohamed Lotfi Efrit b , Hedi M’rabet b,⇑ , Damien Prim a,⇑ a Université de Versailles Saint Quentin-en-Yvelines, Institut Lavoisier de Versailles—UMR CNRS 8180, 45, avenue des Etats-Unis, 78035 Versailles, France b Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de synthèse Organique et Hétérocyclique, 2092 Tunis, Tunisia article info Article history: Received 12 January 2015 Revised 5 February 2015 Accepted 10 February 2015 Available online 16 February 2015 Keywords: Allylphosphonate Coumarin Quinolinone Benzoxepinone abstract An efficient and selective synthesis of Z-(het)arylallylphosphonates is described. The versatile Pd-assisted process also allowed polyarylation sequences leading to star-shaped and binaphthyl derivatives. The methodology could be extended to the preparation of new phosphonomethyl-coumarin, -quinolinone, and -benzoxepinone architectures in high yields. Ó 2015 Elsevier Ltd. All rights reserved. Introduction Phosphonates are an important class of organic compounds that exhibit various bioorganic and medicinal properties such as antimicrobial, antimalarial, or enzyme inhibition. 1 The modulation of such properties can be envisioned through the installation of various substituents in a, b, c-positions to the phosphonate group. In this context, 2-phosphonomethyl acrylates emerged as powerful intermediates, taking advantage of the twice-activated double bond induced by the presence of both phosphonomethylene and carboxylate groups. The installation of various (hetero)nucle- ophiles can thus take place through Michael-type additions leading to c-substituted-2-phosphonomethyl acrylates. 2 The installation of aryl groups in c-position of the phosphonate backbone is also of high interest giving access to cinnamylphosphonate derivatives. 3-Aryl-2-phosphonomethyl acrylates are usually considered as precursors of 3-phosphono-2-alkylpropionoic acid derivatives in model catalytic hydrogenation reactions. 3 The preparation of 3-aryl-2-phosphonomethyl acrylates rely mainly on Baylis Hillman strategy. Allylic acetates derived therefrom undergo addition of phosphorous-based nucleophiles to give stereoselectively the (Z)- 3-aryl-2-phosphonomethyl acrylates (Scheme 1i). 4 3-Substituted- 2-phosphonomethyl acrylates can also be prepared by treatment of Baylis–Hillman adduct with FeCl 3 and trialkyl phosphites (Scheme 1ii). 5 Although limited to phenyl or dichlorophenyl aro- matics, appealing arylation under Pd-catalyzed oxidative process has also been described recently (Scheme 1iii). 6 We have been deeply involved in the construction of allylphos- phonates bearing additional carboxylate groups and on further development of methods that rely on addition reactions. 2 We were interested in the installation of aromatics at the allylphosphonates 1 core through Pd-catalyzed arylation and whether the normal Heck-reaction course could be glanced to the construction of var- ious fused heterocycles by using the carboxylate function located Ar CO 2 R PO(OR') 2 CO2R OAc Ar P(OR') 3 (i) Ph CO 2 R PO(OR) 2 (ii) ArH, PivOH [Pd], [Ag], Ph CO 2 R PO(OR) 2 Ar minor Ph CO 2 R PO(OR) 2 Ar major CO2R OH Ar + P(OR') 3 FeCl 3 (ii) Scheme 1. Main access to 3-aryl-2-phosphonomethyl acrylates. http://dx.doi.org/10.1016/j.tetlet.2015.02.038 0040-4039/Ó 2015 Elsevier Ltd. All rights reserved. ⇑ Corresponding authors. Tel.: +33 1 39 25 44 54; fax: +33 1 39 25 44 52. E-mail addresses: mrabet.fst@gmail.com (H. M’rabet), damien.prim@uvsq.fr (D. Prim). Tetrahedron Letters 56 (2015) 1679–1681 Contents lists available at ScienceDirect Tetrahedron Letters journal homepage: www.elsevier.com/locate/tetlet