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Palladium-Catalyzed Tandem Allylic Substitution/Cyclization and Cascade

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Palladium-Catalyzed Tandem Allylic Substitution/Cyclization and Cascade RSC Advances PAPER View Article Online View Journal | View Issue Palladium-catalyzed tandem allylic substitution/ cyclization and cascade hydrosilylated reduction: Cite this: RSC Adv.,2018,8, 22944 the influence of reaction parameters and hydrosilanes on the stereoselectivity† Peng-Wei Long,a Jian-Xing Xu,a Xing-Feng Bai,ab Zheng Xu,*a Zhan-Jiang Zheng,a Ke-Fang Yang,a Li Lia and Li-Wen Xu *ab To shed light on the influence of reaction parameters on palladium-catalyzed tandem allylic alkylation in the presence of Fei-Phos (a chiral trans-1,2-diaminocyclohexane-derived phosphine ligand), the effect of different phosphine ligands, inorganic or organic bases, Brønsted acids, and other additives on the asymmetric palladium-catalysed alkylation of catechol with allylic diacetate was investigated. In this Received 8th April 2018 reaction, 2-vinyl-2,3-dihydro-benzo[1,4]dioxin products with promising enantioselectivity were achieved Accepted 12th June 2018 in good yields. In addition, a novel palladium-catalyzed three-component and one-pot allylic Creative Commons Attribution-NonCommercial 3.0 Unported Licence. DOI: 10.1039/c8ra02995d substitution/cyclization/reduction reaction assisted by methylphenylsilane was reported with good rsc.li/rsc-advances selectivity. Introduction reactivity substrates for catalytic asymmetric allylic substitution reactions with improved activity and stereoselectivity. Despite Transition-metal-catalyzed allylic substitution reactions are an the recent success in allylic alkylation of various carbon- or extremely useful class of organic transformation, revealed heteroatom-based nucleophiles, including cyanoacetate, alco- 6 several decades ago, and offer simple and practical approaches hols, and heterocycles, transition-metal-catalyzed asymmetric This article is licensed under a for the synthesis of alkene-substituted molecular frameworks.1 allylic substitutions of functional molecules with structurally Notably, the allylic substitution reaction has been proven to be varied allylic acetates continue to receive much attention from one of the most important and fundamental C–C bond-forming synthetic chemists. Thus the development of new reaction Open Access Article. Published on 22 June 2018. Downloaded 10/2/2021 7:11:48 AM. processes in organic synthesis.2 In this regard, the catalytic systems with good yields and stereoselectivity is a valuable topic asymmetric version of allylic alkylation has also become and is still highly desirable. a powerful carbon–carbon or carbon–heteroatom bond-forming Among allylic substitution reactions, the stereoselective approach to a range of structurally diverse allyl-substituted allylic alkylation of oxygen-nucleophiles, such as alcohols, is compounds. These are prevalent functional molecules and one of the most important C–O bond-forming transformations 7 building blocks for the construction of natural products and for the construction of chiral ether-containing compounds. biologically important complexes in synthetic chemistry.3 In Notably, in this context, palladium complexes with bidentate this approach, it is well-known that catalytic asymmetric allylic phosphine or phosphite ligands have been proven to be effec- substitution largely relies on the capability for stereoselective tive catalysts for the construction of different C–O bonds and 7 induction of the chiral ligands.4 In fact, numerous phosphine chiral ethers with good stereoselectivity. For example, we ligands have been utilized as they are extremely effective and are developed the chiral trans-1,2-diaminocyclohexane-derived key factors in this allylic substitution reaction, including allylic multiple stereogenic and multifunctional CycloN2P2-Phos cyclization.1–5 However, it is still highly desirable to search for (also called Fei-Phos) for catalytic asymmetric allylic substitu- 8 a highly efficient ligand, which is needed to accommodate low- tions of benzyl alcohols and silanols with allylic acetates. Good to excellent yields and high enantioselectivities (up to 99% ee) were achieved in this reaction, which motivated us to expand a Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of the synthetic functions of Fei-Phos in palladium catalysis.9 Education, Hangzhou Normal University, Hangzhou 311121, P. R. China. E-mail: [email protected]; Fax: +86 2886 5135; Tel: +86 2886 5135 Although asymmetric palladium-catalyzed allylic alkylation of bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of catechol with (Z)-2-butene-1,4-diylbis(methylcarbonate) gave Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China. E-mail: the desired 2-vinyl-1,4-benzodioxane with up to 45% ee in the [email protected] presence of chiral ligands such as BINAP was realized by Sinou † Electronic supplementary information (ESI) available. See DOI: in 1994,10 the use of simple allylic acetates as the electrophiles 10.1039/c8ra02995d 22944 | RSC Adv.,2018,8, 22944–22951 This journal is © The Royal Society of Chemistry 2018 View Article Online Paper RSC Advances in this reaction has not been described yet. In addition, it is phosphine ligands are summarized in Table 1. Notably, most of surprising that limited progress has been made so far on the the phosphine ligands gave poor or no yield of the corre- tandem allylic alkylation of catechol with allylic reagents for the sponding product 3a. Only L3, L8, and L12 (Fei-Phos) were synthesis of chiral 2-vinyl-2,3-dihydro-benzo[1,4]dioxanes.11 proven to be effective in this reaction (entries 3, 8, and 12, Thus in this work, we continue to carry out further investiga- respectively), and L3 and L8 gave low to moderate yields (30– tions on the catalytic asymmetric allylic substitution of catechol 50%) as well as low enantioselectivity (25–39% ee). Interest- with allylic diacetates in the presence of a palladium catalyst ingly, our Fei-Phos is still the best choice in this reaction in with Fei-Phos or other P-ligands. This approach could be useful comparison with the other P-ligands evaluated in this work for the construction of 1,4-benzodioxane ring systems that are (entry 12, 60% yield and 39% ee). Notably, when the reaction found in various natural products and are key skeletons in temperature was decreased to 0 or À20 C, both the yield and pharmaceutical candidates possessing important biological enantioselectivity decreased obviously (entries 17 and 18). With activities.12 In addition, the effect of various phosphine ligands, the optimized ligand in THF, the solvent effect was also evalu- inorganic or organic bases, Brønsted acids, and other additives, ated in the catalytic asymmetric allylic substitution/cyclization on the asymmetric palladium-catalysed alkylation of catechol reaction (Table 1, entries 19–22). Although this tandem allylic with allylic diacetate was investigated in this work. substitution reaction occurred smoothly to deliver 2-vinyl-2,3- dihydro-benzo[1,4]dioxane (3a) with good yields (70%) in 1,4- Results and discussion dioxane, the solvents evaluated in this work gave inferior performance in comparison with THF. Palladium-catalyzed tandem allylic alkylation of catechol with Then, we continued to investigate the effect of the palladium allylic compounds catalyst precursors or other transition metal catalysts on the Firstly, the allylic substitution/cyclization reaction of benzene- 1,2-diol 1a with the (Z)-but-2-ene-1,4-diol-derived allylic acetate 2a was used as a model reaction at room temperature in Table 1 The effect of the various phosphine ligands on the palladium- Creative Commons Attribution-NonCommercial 3.0 Unported Licence. the presence of a palladium complex which was generated in catalyzed allylic substitution/cyclization reaction of benzene-1,2-diol 1a with the (Z)-but-2-ene-1,4-diol derived allylic acetate 2a situ by mixing Pd2(dba)3 [tris(benzylideneacetone)dipalladium] with various phosphine ligands (Scheme 1). It should be noted that there is no effective phosphine ligand previously reported for this reaction.10,11 To evaluate the feasibility of the tandem allylic alkylation reactions, we wanted to explore the potential of commercially available phosphine ligands and our P-ligands, which we have reported in the past few years,13 including Fei- This article is licensed under a Phos. Results from the optimization studies employing the Entrya Ligand Solvent Yieldd (%) eee, f (%) 1 L1 THF n.r — Open Access Article. Published on 22 June 2018. Downloaded 10/2/2021 7:11:48 AM. 2 L2 THF <5 — 3 L3 THF 50 39 4 L4 THF n.r — 5 L5 THF n.r — 6 L6 THF n.r — 7 L7 THF n.r — 8 L8 THF 30 25 9 L9 THF n.r — 10 L10 THF n.r — 11 L11 THF n.r — 12 L12 THF 60 39 13 L13 THF n.r — 14 L14 THF n.r — 15 L15 THF n.r — 16 L16 THF n.r — 17b L12 THF 24 31 18c L12 THF 5 33 19 L12 1,4-Dioxane 72 35 20 L12 DCM <5 — 21 L12 DCE 12 n.d 22 L12 DMSO n.r — a Reaction conditions: 1a (0.25 mmol), 2a (1.4 eq.), Pd2(dba)3 (2.5 mol%) b c and Fei-Phos (5 mol%), N2, rt, 24 h. The temperature was 0 C. The temperature was À20 C. d Isolated yields aer silica gel Scheme 1 The various phosphine ligands evaluated in the palladium- chromatography. e Determined using chiral HPLC. n.r is no reaction; catalyzed tandem allylic alkylation of benzene-1,2-diol 1a with the (Z)- a trace is represented by <5% yield; n.d is not determined. but-2-ene-1,4-diol derived allylic acetate 2a. f Determined by the sign of the specic rotation.14 This journal is © The Royal Society of Chemistry 2018 RSC Adv.,2018,8, 22944–22951 | 22945 View Article Online RSC Advances Paper catalytic asymmetric allylic alkylation. As shown in Table 2, most of the palladium salts were not suitable for this tandem h allylic alkylation reaction, in which only [Pd( -C3H5)Cl]2 and Pd(PPh3)4 had the ability to promote tandem allylic substitution to give the corresponding 2-vinyl-2,3-dihydro-benzo[1,4]dioxane (3a) in moderate yield (35–58%).
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