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- Copyright © 2019 Toshihiro Murafuji et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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Abstract
Hindawi Heteroatom Chemistry Volume 2019, Article ID 2385064, 7 pages https://doi.org/10.1155/2019/2385064 Research Article One-Pot Synthesis of Hypervalent Diaryl(iodo)bismuthanes from o-Carbonyl Iodoarenes by Zincation 1,2 2 3 1 Toshihiro Murafuji , A. F. M. Hafizur Rahman, Daiki Magarifuchi, Masahiro Narita, 1,3 1,3 1,3 Isamu Miyakawa, Katsuya Ishiguro, and Shin Kamijo Graduate School of Sciences and Technology for Innovation, Yamaguchi University, Yamaguchi 753-8512, Japan Graduate School of Medicine, Yamaguchi University, Yamaguchi 753-8512, Japan Graduate School of Science and Engineering, Yamaguchi University, Yamaguchi 753-8512, Japan Correspondence should be addressed to Toshihiro Murafuji; murafuji@yamaguchi-u.ac.jp Received 31 October 2018; Accepted 22 January 2019; Published 27 February 2019 Academic Editor: Oscar Navarro Copyright © 2019 Toshihiro Murafuji et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Diaryl(iodo)bismuthanes possessing a hypervalent C=O∙∙∙Bi–I bond were conveniently synthesized in a one-pot reaction by using arylzinc reagents generated from o-carbonyl iodobenzenes and zinc powder under ultrasonication. iTh s method is superior to the conventional organolithium and Grignard methods because it has a wide functional group tolerance, requires no protecting group manipulations, and proceeds under mild reaction conditions that do not need low temperature control. Furthermore, no intermediate triarylbismuthane precursor for the hypervalent iodobismuthane is necessary. 1. Introduction their reactions with BiI and ArBiX , respectively. Further- 3 2 more, the acetyl substituent of acetophenone is incompatible Much effort has been devoted to the study of hypervalent bis- with BuLi, meaning that the synthesis of started from the muth(III) compounds [1–5]. Hypervalent bonds are formed protected silyl enol ether, and the harsh reaction conditions efficiently via intramolecular coordination of a neutral donor requiring excess BuLi caused the loss of Ar BiCl or the decomposition of the product, lowering the reproducibility of to a bismuth(III) center [6–12]. We have used this method to synthesize various hypervalent organobismuth(III) com- the yield [13, 14]. To facilitate the search for active antifungal pounds stabilized by intramolecular coordination and have compounds, a general and convenient synthetic method characterized their molecular structures [13]. Furthermore, that has wide functional group compatibility for introducing we have revealed that these compounds show antifungal various molecular scao ff lds to the bismuth(III) center is activities against the yeast Saccharomyces cerevisiae [14, 15]. required. In particular, compounds and , which possess diary sulfone We have reported the synthesis under Grignard con- and acetophenone molecular scaffold, respectively, exhibited ditions of p-substituted triarylbismuthanes and , which have a formyl and ester substituent, respectively (Scheme 2) high antifungal activities. These compounds are synthesized by directed ortho- [16]. eTh imino and ester substituents were tolerated despite lithiation (Scheme 1). Directed lithiation is a very useful their polarized double bond, although required protection of the formyl substituent and needed low-temperature and reliable synthetic method for introducing a molecular scaffold bearing an ortho-coordinative functional group, control. Based on these results, we investigated using a although the method can suffer from various practical dif- type of organometallic reagent that is less reactive than ficulties. For example, the synthesis of and used triaryl- Grignard reagents. Such an organometallic reagent would bismuthane as a precursor because the ortho-functionalized be compatible with carbonyl functional group and thus a aryllithiums were too reactive to give and directly through suitable synthetic tool for use in our desired general method. 2 Heteroatom Chemistry ／ ／ ／ 2 2 2 1) BuLi or LTMP S S S Ar 2) ４ＩＦ＂Ｃ＃Ｆ ） Ar Ar Ar Bi Bi Tol I Me Me LTMP = Me Me Tol = 4-－？＃ （ 6 4 Li －？ ３Ｃ／ Me Me Me 3 －？ ３Ｃ＃Ｆ 1) ！Ｌ ＂Ｃ＃Ｆ 1) ＂＆ ∙／％Ｎ 3 BuLi (excess) 2 3 2 ％Ｎ ．, NaI 2) NaX 3 TMEDA 2) （ ／ 2 O O MeCN Hexane ＂Ｃ！Ｌ Bi Ar 2 X Scheme 1: Synthesis of and by directed lithiation. NPr-i i-PrMgBr ＂Ｃ＃Ｆ then （ ／ 3 2 I Bi THF, 25 C H O OEt OEt i-PrMgBr ＂Ｃ＃Ｆ then （ ／ 3 2 Bi THF, −40 C Scheme 2: Synthesis of and . Several mild bismuth–carbon bond forming reactions (7.26 ppm, 77.0 ppm) and DMSO (2.50 ppm, 40.45 ppm). have been reported, which include the treatment of aryl IR spectra were obtained as KBr pellets on a Nico- iodides with bismuth shot in the presence of Cu and CuI by let FT-IR Impact 410 spectrophotometer. Melting points ball milling [17], the arylation of bismuth(III) carboxylates were determined on a YANAGIMOTO melting point by sodium tetraarylborate [18], and the reaction of BiCl apparatus without correction. Elemental analysis was per- with organozinc reagents [19]. To achieve wide functional formed on a MICRO CORDER JM10 apparatus (J-SCIENCE group tolerance, we chose organozinc reagents because they LAB. Co.). HRMS were recorded on a Bruker Dalton- are compatible with carbonyl functionalities such as ester, ics micrOTOF II (APCI) instrument. 2 -Iodoacetophenone acetyl, and even formyl substituents, and the chemistry and ethyl 2-iodobenzoate were commercially available. 2- of thesereagentsiswellestablished[20–22]. Herein,we Iodobenzaldehyde, 4-fluoro-2-iodobenzaldehyde, 2-iodo-5- report the synthesis of hypervalent iodobismuthanes a and methoxybenzaldehyde, 4 -fluoro-2 -iodoacetophenone, and a–a, which contain a carbonyl group, by zincation of 3-iodothiophene-2-carboxaldehyde were prepared in high the corresponding iodoarenes (Scheme 3). The organozinc yields by Finkelstein reaction of the corresponding bro- method was superior to our previously reported organo- moarenes in accordance with the literature [23]. lithium and Grignard methods owing to the high functional group tolerance, short synthesis, mild reaction conditions, 2.1. Typical Procedure for the Finkelstein Reaction of Bro- and acceptable yields. moarenes. To a round-bottomed flask (50 mL) equipped with a magnetic stir bar were added bromoarene (2.5 mmol), CuI (5 mol%), NaI (5 mmol), and 1,3-diaminopropane (10 2. Materials and Methods mol%). After dry 1,4-dioxane (2.5 mL) was added to the All of the reactions were carried out under argon unless flask, the mixture was refluxed for 24 h. eTh reaction was otherwise noted. N,N-Dimethylformamide (DMF) was dis- quenched with water (30 mL) at room temperature and the tilled from calcium hydride under reduced pressure. 1,4- resulting mixture was extracted with ethyl acetate (3× 30 Dioxane was distilled from calcium hydride. Diethyl ether mL). eTh organic layer was dried (Na SO ) and concentrated 2 4 was distilled from benzophenone ketyl before use. Hand to leave a residue, which was chromatographed on silica gel C NMR spectra were recorded in CDCl or DMSO- with hexane–ethyl acetate (5:1) to give the corresponding d on a BRUKER AVANCE 400S spectrometer. Chemical iodoarene, which was used in the next step without further shifts were referenced to residual solvent peak: chloroform puricfi ation. Heteroatom Chemistry 3 Me H OEt MeO O O Bi Tol X X Bi Tol Bi Tol Bi Tol Bi Tol I I 2a: X = H 6a: X = H 8a 10a 9a 5a: X = F 7a: X = F Scheme 3: Hypervalent iodobismuthanes functionalized with a carbonyl group. 2.2. 2-Iodobenzaldehyde. Yield 99% (574 mg, 2.48 mmol), mL). eTh combined extracts were concentrated to leave ∘ 1 an oily residue, which was chromatographed on silica gel Colorless solid, mp 39–41 C. H NMR (400 MHz, CDCl ): with hexane–ethyl acetate (5:1) to ao ff rd the corresponding 𝛿 7.29 (1H, dt, J = 7.6 Hz, 1.6 Hz), 7.47 (1H, t, J =7.6Hz),7.89 iodobismuthane. (1H, dd, J = 7.6 Hz, 1.6 Hz), 7.96 (1H, d, J = 8.0 Hz), 10.08 (1H, s). 2.8. (2-Acetylphenyl)iodo(4-methylphenyl)bismuthane 2a. 2.3. 4-Fluoro-2-Iodobenzaldehyde. Yield 97% (606 mg, 2.43 Yellow crystal, Yield 35% (191 mg, 0.35 mmol), mp 160–162 C. ∘ 1 1 mmol), Colorless solid, mp 49–51 C. H NMR (400 MHz, H NMR (400 MHz, CDCl ):𝛿 2.25 (3H, s), 2.69 (3H, s), CDCl ):𝛿 7.19 (1H, m), 7.68 (1H, m), 7.91 (1H, m), 9.99 (1H, 7.25 (2H, d, J = 8.0 Hz), 7.71 (1H, dt, J = 7.6 Hz, 1.2 Hz), 7.88 d, J =2.4 Hz). (1H, dt, J = 7.6 Hz, 1.2 Hz), 8.07 (2H, d, J = 8.0 Hz), 8.22 (1H, dd, J = 7.6 Hz, 1.2 Hz), 9.41 (1H, dd, J = 7.2 Hz, 0.8 Hz). C NMR (100 MHz, CDCl ):𝛿 21.54, 27.08, 128.50, 132.36, 134.51, 2.4. 2-Iodo-5-Methoxybenzaldehyde. Yield 98% (642 mg, 3 ∘ 1 138.01, 138.21, 138.98, 143.10, 145.55, 166.78, 172.09, 207.54. IR 2.45 mmol), Colorless solid, mp 113–116 C. HNMR (400 −1 (KBr): ] 3738, 3037, 1622, 1552, 1276 and 761 cm .HRMS MHz, CDCl ):𝛿 3.84 (3H, s), 6.92 (1H, dd, J = 8.4 Hz, 3.2 (APCI) calcd. for C H BiIO: [M–H] 544.9832. found: 15 13 Hz), 7.43 (1H, d, J = 3.2 Hz), 7.80 (1H, d, J = 8.4 Hz), 10.02 (1H, 544.9821. s). 2.9. (2-Acetyl-5-fluorophenyl)iodo(4-methylphenyl)bismu- 2.5. 4 -Fluoro-2 -Iodoacetophenone. Yield 98% (647 mg, 2.45 ∘ 1 thane 5a. Yellow crystal, Yield 28% (158 mg, 0.28 mmol), mp mmol), Colorless solid, mp 45–46 C. H NMR (400 MHz, ∘ 1 186–188 C. H NMR (400 MHz, DMSO-d ):𝛿 2.19 (3H, s), CDCl ):𝛿 2.59(3H,s),7.11(1H,m), 7.52(1H,m),7.65(1H,m). 6 2.72 (3H, s), 7.29 (2H, d, J = 7.6 Hz), 7.54 (1H, dt, J =8.4 Hz, 2.0 Hz), 8.11 (2H, d, J = 7.6 Hz), 8.55 (1H, dd, J = 8.4 Hz, 4.8 2.6. 3-Iodothiophene-2-Carboxaldehyde. Yield 99% (589 mg, Hz), 8.89 (1H, br-s). C NMR (100 MHz, DMSO-d ):𝛿 21.13, ∘ 1 2.48 mmol), Colorless solid, mp 82–85 C. HNMR(400 27.48, 115.62 (d, J = 22.6 Hz), 130.94 (br-d), 132.08(×2), 137.09, MHz, CDCl ):𝛿 7.28 (1H, d, J = 4.8 Hz), 7.70 (1H, dd, J =4.8 138.45, 138.85 (d, J = 8.0 Hz), 140.51, 169.52, 172.12, 207.85. Hz, 1.2 Hz), 9.83 (1H, d, J =1.2 Hz). −1 IR (KBr): ] 1620, 1575, 1558, 1358, 1299, 1262 and 1201 cm . HRMS (APCI) calcd. for C H BiFIO: [M–H] 562.9730. 15 12 2.7. Typical Procedure for the Synthesis of Aryl(iodo)(4- found: 562.9726. methylphenyl)bismuthane. To a round-bottomed flask (50 mL) equipped with a magnetic stir bar were added 2.10. (2-Formylphenyl)iodo(4-methylphenyl)bismuthane 6a. bismuth(III) chloride (422 mg, 1.33 mmol) and tris(4- Yellow crystal, Yield 56% (298 mg, 0.56 mmol), mp methylphenyl)bismuthane (323 mg, 0.67 mmol). Aeft r ∘ 1 143–144 C. H NMR (400 MHz, DMSO-d ):𝛿 2.21 (3H, s), dry diethyl ether (6 mL) was added to the flask at room 7.30 (2H, d, J = 7.6 Hz), 7.86 (1H, t, J = 7.2 Hz), 7.95 (1H, t, J temperature, the mixture was stirred for 1 h. To another = 7.2 Hz), 8.14 (2H, d, J= 7.6Hz),8.44(1H,d, J =7.2Hz), round-bottomed flask (50 mL) were added iodoarene (1 9.02 (1H, d, J = 7.2 Hz), 10.75 (1H, s). C NMR (100 MHz, mmol), zinc powder (262 mg, 4 mmol), and dry DMF (5 CDCl ):𝛿 21.55, 128.65, 132.47, 137.58, 138.23, 138.44, 139.63, mL). eTh flask was set in an ultrasonic water bath at room 143.66, 146.16, 165.99, 170.92, 199.50. IR (KBr): ] 3058, 2857, temperature (25 C) and the resulting mixture was sonicated −1 1633, 1572, 1553, 1296 and 1207 cm .HRMS(APCI)calcd. for 1.5–4 h, during which time the water bath temperature for C H BiIO: [M+H] 532.9808. found: 532.9810. 14 13 rose to 48 C. The sonication was stopped and unreacted zinc powder precipitated. eTh resulting supernatant solution 2.11. (2-Formyl-5-fluorophenyl)iodo(4-methylphenyl)bismu- containing an arylzinc reagent was slowly transferred to the thane 7a. Yellow crystal, Yield 29% (195 mg, 0.29 mmol), mp suspension of dichloro(4-methylphenyl)bismuthane (ca. 2 ∘ 1 mmol) thus formed, and the resulting mixture was stirred 148–149 C. H NMR (400 MHz, DMSO-d ):𝛿 2.21 (3H, s), for 3.5–8 h at room temperature. eTh reaction was quenched 7.32 (2H, d, J = 7.6 Hz), 7.61 (1H, dt, J = 8.4 Hz, 2.4 Hz), 8.18 with a saturated aqueous solution of NaI (3 mL) and the (2H, d, J = 7.6 Hz), 8.52 (1H, dd, J = 8.0 Hz, 5.2 Hz), 8.74 (1H, resulting mixture was extracted with ethyl acetate (3× 50 d, J = 6.4 Hz), 10.74 (1H, s). C NMR (100 MHz, DMSO-d ): 6 4 Heteroatom Chemistry H OLi H 1) BuLi (excess) 1) ＂＆ ∙／％Ｎ 3 2 LiN N Me 2) ！Ｌ ＂Ｃ＃Ｆ then （ ／ 2) NaX 2 2 O O Benzene Bi Ar ＂Ｃ！Ｌ Me 6 X Scheme 4: Conventional synthesis of by directed lithiation. 𝛿 21.14, 115.75 (d, J = 22.7 Hz), 131.83 (br-s), 132.17(×2), 137.05, at theorthoposition in thepresenceofzincpowder under 139.01,140.73(d, J = 9.0 Hz), 140.88, 169.19, 171.80, 199.67. ultrasonication at 30 C. −1 IR (KBr): ] 3061,2875, 1638,1582, 1561,1259and 1204 cm . When a mixture obtained by sonicating ethyl 2- − ∘ HRMS (APCI) calcd. for C H BiFIO: [M–H] 548.9566. iodobenzoate with zinc powder (1 equiv) at 25 CinDMF 14 10 found: 548.9570. was allowed to react with TolBiCl (1 equiv), a was obtained in only 4% yield (Table 1, Entry 1). eTh poor yieldwas attributed totheincompleteconversionofthe 2.12. (2-Formyl-4-methoxyphenyl)iodo(4-methylphenyl)bis- starting iodoarene to the arylzinc. eTh yield of a was muthane 8a. Yellow crystal, Yield 31% (175 mg, 0.31 mmol); increased by increasing the equivalents of zinc powder ∘ 1 mp 146–147 C; H NMR (400 MHz, DMSO-d ):𝛿 2.22 (3H, and TolBiCl (Entries 2 and 3). Furthermore, an increase s), 3.87 (3H, s), 7.31 (2H, d, J = 8.0 Hz), 7.48 (1H, dd, J =7.6 ∘ in the temperature from 25 to 48 Cduringthesonication Hz, 2.8 Hz), 7.99 (1H, d, J = 2.8 Hz), 8.13 (2H, d, J =7.6 Hz), accelerated the zincation reaction (Entries 4–9). The reaction 8.78 (1H, d, J = 8.0 Hz), 10.66 (1H, s). C NMR (100 MHz, mixture turned dark yellow during the zincation, which was CDCl ):𝛿 21.57, 55.67, 122.95, 125.69, 132.38, 138.20, 138.31, a good indicator for the completion of the reaction. eTh 145.09, 147.94, 160.26, 161.34, 166.38, 199.13. IR (KBr): ] 3027, yield of a was sensitive to the zinc powder loading and the –1 2924, 2862, 1640, 1585, 1552, 1460, 1251 and 1044 cm .HRMS best result was obtained when 4 equiv zinc powder and 2 (APCI) calcd. for C H BiIO :[M–H] 560.9770. found: 15 13 2 equiv TolBiCl were used (Entry 7). Higher zinc powder or 560.9770. TolBiCl loadings decreased the yield of a (Entries 8 and 9). 2.13. (2-Formyl-3-thienyl)iodo(4-methylphenyl)bismuthane Encouraged by the success of the one-pot synthesis of a, 9a. Yellow crystal, Yield 53% (287 mg, 0.53 mmol), mp we performed the one-pot syntheses of a and a,which have ∘ 1 an acetophenone scaffold, using the reaction conditions used 132–133 C. H NMR (400 MHz, CDCl ):𝛿 2.28 (3H, s), 7.31 in the synthesis of a (Table 1, Entry 7). After the zincation (2H, d, J = 7.6 Hz), 8.04 (1H, d, J = 4.4 Hz), 8.09 (1H, d, J = reaction mixtures had turned dark yellow, the arylzinc was 4.4Hz),8.14(2H,d, J = 7.6 Hz), 10.12 (1H, s). CNMR (100 allowed to react with TolBiCl , followed by quenching with a MHz, CDCl ):𝛿 21.58, 132.67, 138.50, 138.56, 142.08, 145.66, saturated aqueous solution of NaI to give a and a in 35% 148.47,166.97, 174.32,186.44. IR (KBr): ] 1586, 1483, 1450, −1 and 28% yields, respectively, despite the presence of acidic 1397, 1337, 1195, 853 and 794 cm .HRMS(APCI)calcd.for acetyl protons (Table 2, Entries 1 and 2). We have previously C H BiIOS: [M+H] 538.9374. found: 538.9374. 12 11 reported that the synthesis of a from the corresponding silyl enol ether by conventional directed lithiation failed 2.14. (2-Ethoxycarbonylphenyl)iodo(4-methylphenyl)bismu- (Scheme 1) [14]. We explained the failure by the presence of thane 10a. Yellow crystal, Yield 61% (351 mg, 0.61 mmol), the uo fl ro substituent, which can act as a directing group. eTh ∘ 1 mp 125–126 C. H NMR (400 MHz, CDCl ):𝛿 1.40 (3H, t, success in obtaining a demonstrates the usefulness of the J = 7.2 Hz), 2.26 (3H, s), 4.43 (2H, m), 7.26 (2H, d, J =7.6 zincation method. Hz), 7.36 (1H, dt, J = 7.6 Hz, 0.8 Hz), 7.84 (1H, dt, J =7.6Hz, Furthermore, we used this method to synthesize a– a, 1.2 Hz), 8.09 (2H, d, J = 7.6 Hz), 8.22 (1H, dd, J =7.6Hz,1.2 which have a formyl substituent (Entries 3–6). We have Hz), 9.43 (1H, d, J =7.2 Hz). C NMR (100 MHz, CDCl ): previously reported the synthesis of by the directed ortho- 𝛿 14.09, 21.54, 63.31, 128.29, 132.28, 132.77, 134.35, 137.96, lithiation of lithium𝛼-amino alkoxide (Scheme 4) [13]. This 138.27, 138.70, 143.83, 166.84, 169.52, 175.85. IR (KBr): ] 2990, method required excess BuLi, which oeft n caused the loss −1 1634, 1573, 1373, 1311, 1005, 785 and 733 cm .Anal. Calc.for of Ar BiCl ordecompositionoftheproductbyoverreaction C H BiIO : C, 33.35; H, 2.80. Found: C, 33.32; H, 3.03. 16 16 2 with unreacted BuLi. In addition, the lithium alkoxide moi- ety could form an undesired bismuth alkoxide by reacting with Ar BiCl. Hence, the present zincation overcomes these 3. Results and Discussion drawbacks. In particular, a, a,and a were obtained in acceptable yields by the zincation; if conventional directed Initially, we tried the one-pot synthesis of a by the zincation of ethyl 2-iodobenzoate. The arylzinc was prepared by using lithiation was used, the u fl oro and methoxy substituents in themethodreportedbyTakagiandcoworkers[20], who a and a, respectively, would act as directing groups and the treated iodoarenes containing an electron-withdrawing sub- thienyl ring proton𝛼 to the sulfur atom in a would undergo stituent, such as a methoxycarbonyl or an acetyl substituent, undesired lithiation. Heteroatom Chemistry 5 Table 1: Optimization of the reaction conditions for the synthesis of a. OEt OEt 1) ４ＩＦ＂Ｃ＃Ｆ , 8 h, r.t. Zn 2) NaI (aq) O O 10a Ultrasound ZnI DMF Entry Zn TolBiCl Ultrasound Ultrasound Yield (%) (equiv) (equiv) Temp ( C) Time (h) a 11.0 1.0 25 6 4 21.5 1.0 25 6 9 32.0 1.5 25 5 14 42.5 1.5 25–48 3 18 5 3.0 2.0 25–48 4 28 6 3.5 2.0 25–48 4 41 7 4.0 2.0 25–48 4 61 8 4.5 2.0 25–48 5 60 9 4.0 3.0 25–48 5 55 Table 2: Synthesis of iodobismuthanes. NaI (aq ) ４ＩＦ＂Ｃ＃Ｆ Zn ArI ArZnI ArBi(Tol)I Ultrasound, DMF 25−48 C Ultrasound TolBiCl Entry ArI ArBi(Tol)I Yield (%) Time (h) Time (h) Me 1 O 2.0 3.5 a 35 Me 2 1.5 6.0 a 28 3 3.5 8.0 a 56 4 3.0 8.0 a 29 F I MeO 5 3.5 8.0 a 31 6 4.0 8.0 a 53 I 6 Heteroatom Chemistry The molecular structure of (Ar = Tol, X = Br) has References been characterized by X-ray structure analysis and CNMR [1] X. Chen, Y. Yamamoto, and K.-Y. 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