Facile and innovative catalytic protocol for intramolecular Friedel–Crafts cyclization of Morita–Baylis–Hillman adducts: Synergistic combination of chiral (salen)chromium(III)/BF₃·OEt₂ catalysis

• Karthikeyan Soundararajan,
• Helen Ratna Monica Jeyarajan,
• Raju Subimol Kamarajapurathu and
• Karthik Krishna Kumar Ayyanoth

Beilstein J. Org. Chem. 2021, 17, 2186–2193, doi:10.3762/bjoc.17.140

• .17.140 Abstract The chiral (salen)Cr(III)/BF3·OEt2 catalytic combination was found to be an effective catalyst for intramolecular Friedel–Crafts cyclization of electron-deficient Morita–Baylis–Hillman adducts. In presence of mild reaction conditions the chiral (salen)Cr(III)/BF3·OEt2 complex affords 2

• -substituted-1H-indenes from unique substrates of Morita–Baylis–Hillman adducts via an easy operating practical procedure. Keywords: boron trifluoride etherate; chiral (salen)chromium(III); intramolecular Friedel–Crafts cyclization; Morita–Baylis–Hillman adducts; substituted-1H-indenes; Introduction

• -deficient arenes [4][5][6][7]. Operating FC reactions in versatile synthons such as Morita–Baylis–Hillman (MBH) adducts is a challenging process. Inter/intramolecular Friedel–Crafts reactions of Morita–Baylis–Hillman adducts leads to a variety of products such as quinolinones [8], cycloheptene-6

Azidophosphonium salt-directed chemoselective synthesis of (E)/(Z)-cinnamyl-1H-triazoles and regiospecific access to bromomethylcoumarins from Morita–Baylis–Hillman adducts

• Soundararajan Karthikeyan,
• Radha Krishnan Shobana,
• Kamarajapurathu Raju Subimol,
• J. Helen Ratna Monica and
• Ayyanoth Karthik Krishna Kumar

Beilstein J. Org. Chem. 2020, 16, 1579–1587, doi:10.3762/bjoc.16.130

• powerful synthetic tools. Keywords: halomethylcoumarin; Morita–Baylis–Hillman adducts; organocatalyst; phosphonium salt; triazolation; Introduction The presence of versatile functional groups in close proximity classifies Morita–Baylis–Hillman adducts as privileged key scaffolds for synthetic organic

• ]. Among the known synthetic transformations using functionalized MBH adducts, cycloaddition reactions are challenging and attractive for synthetic organic chemists. In this context, acetate-functionalized Morita–Baylis–Hillman adducts have been extensively utilized over other precursors. For example

• : phosphonium salt-catalysed triazolation of MBH adducts. Scope of the one-pot cascade reaction of the unprotected Morita–Baylis–Hillman adducts 3a–q. Comparative analysis of the sequential one-pot reaction. Optimization of the triazolation of the MBH adduct 1a. Optimization of the reaction conditions for 3

Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system

• Satoshi Okusu,
• Yutaka Sugita,
• Etsuko Tokunaga and
• Norio Shibata

Beilstein J. Org. Chem. 2013, 9, 2189–2193, doi:10.3762/bjoc.9.257

• of 1,4-additive trifluoromethylation of (trifluoromethyl)trimethylsilane (Me3SiCF3, Ruppert–Prakash reagent) to very specific substrates such as trans-1-benzoyl-2-(dimethylamino)ethylene [12], 2-polyfluoroalkylchromones [13][14], isoxazoles with a nitro group at the 4-position [15], and Morita–Baylis

• –Hillman adducts (via SN2’ [16] or successive SN2’/SN2’ mode [17]). Sevenard and co-workers reported the nucleophilic 1,4-trifluoromethylation to chromones, coumarins and cyclohex-2-enone using the Ruppert–Prakash reagent, which was achieved by blocking the carbonyl moiety of the substrates with a bulky

Reactions of nitroxides XIII: Synthesis of the Morita–Baylis–Hillman adducts bearing a nitroxyl moiety using 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a starting compound, and DABCO and quinuclidine as catalysts

• Jerzy Zakrzewski

Beilstein J. Org. Chem. 2012, 8, 1515–1522, doi:10.3762/bjoc.8.171

• Jerzy Zakrzewski Institute of Industrial Organic Chemistry, Annopol 6, 03-236 Warsaw, Poland 10.3762/bjoc.8.171 Abstract The Morita–Baylis–Hillman adducts bearing a nitroxyl moiety were synthesized from 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and aliphatic, aryl and heterocyclic

Synthesis of axially chiral oxazoline–carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe₂

• Feijun Wang,
• Shengke Li,
• Mingliang Qu,
• Mei-Xin Zhao,
• Lian-Jun Liu and
• Min Shi

Beilstein J. Org. Chem. 2012, 8, 726–731, doi:10.3762/bjoc.8.81

• type of axially chiral ligand 7 with an N-naphthyl framework (Figure 2) instead of traditional binaphthyl framework [15]. Their palladium complexes 8 showed high stereoselectivities in asymmetric allylic arylations to achieve the kinetic resolution of Morita–Baylis–Hillman adducts, affording up to 99

• % ee of the (E)-allylation products and 92% ee of the recovered Morita–Baylis–Hillman adducts. These intriguing results stimulated us to further develop the axially chiral oxazoline–carbene ligands 7 with an N-naphthyl framework and to evaluate their coordination with AuCl·SMe2. Results and Discussion