One-Pot Synthesis of β-Hydroxysulfones and Its ... - ACS Publications

Sep 6, 2017 - Preparation of Anticancer Drug Bicalutamide. Yajun Wang, Wei Jiang, and Congde Huo*. Key Laboratory of Eco-Environment-Related Polymer ...
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One-Pot Synthesis of β‑Hydroxysulfones and Its Application in the Preparation of Anticancer Drug Bicalutamide Yajun Wang, Wei Jiang, and Congde Huo* Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, China S Supporting Information *

ABSTRACT: An efficient one-pot multistep strategy has been developed, comprising auto-oxidative difunctionalization of alkenes, oxidation of sulfides, and a further reduction of peroxides for the synthesis of complex β-hydroxysulfone derivatives from phenthiols and alkenes. This method has several advantageous characteristics, including readily available substrates, low-cost and environmental benign reagents, nontoxic and renewable solvents, and mild reaction conditions. The application of this transformation to the multigram-scale preparation of the anticancer drug bicalutamide is accomplished.

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pharmaceutical molecules and are key building blocks in organic synthesis.8 Thus, the development of synthetic approaches for the preparation of structurally diverse βhydroxysulfones is a field of constant interest. Traditionally, β-hydroxysulfones are prepared by the opening of epoxides with sulfinate salts, the reduction of β-oxosulfones, or the hydroxylation of α,β-unsaturated sulfones.9 However, these methods always produce large amounts of byproducts or require multiple steps. Since 2013, the addition of sodium sulfinates or sulfinic acids to alkenes has become a straightforward method to construct this kind of molecules.10 However, this method still has some drawbacks: (1) The commercially available substrates are very limited; sulfinic acids are commercially unavailable (unstable, air sensitive), and only a few sodium sulfinates are commercially available. (2) A stoichiometric amount of triphenylphosphine (PPh3) is often required for the reduction of peroxides, and the removal of the byproduct triphenylphosphine oxide (Ph3PO) is a classical problem, which always requires tedious chromatography.11 Therefore, the development of environmentally benign processes to access β-hydroxysulfones from simple and readily available chemicals is still highly desired. Herein, we report the one-pot synthesis of β-hydroxysulfones from phenthiols and alkenes. This new methodology of green chemistry has several advantages: wide availability of substrates, cheap and environmental benign reagents, the use of ethanol as the sole solvent, and reactions at room temperature or under slight heat. At the outset, p-toluenethiol (1a) and styrene (2a) were selected as the model substrates to optimize the reaction conditions, including the reagents, the solvents, and the reaction temperature. To our delight, the one-pot reaction of styrene with p-toluenethiol in the presence of O2 in ethanol as

ne-pot multistep synthesis is an environmentally and economically friendly methodology for the construction of complex and high-value compounds.1 Through this strategy, the products are obtained without the separation and purification of intermediates, which minimizes production cycles and cost and saves time and resources. Thus, the increasing demands for green and sustainable synthetic processes promote the development of the sequential one-pot synthesis. Oxidation reactions are of great importance in nature and play an important role in organic synthesis. Following the principle of sustainable chemistry, O2 is an environmentally benign oxidant and also an ideal oxygen source for the functionalization of organic molecules, and it has received considerable attention in modern oxidation chemistry.2 Recently, auto-oxidation-involved transformations have captured growing attention from organic chemists, and interesting progress has been made.3 Oxone is a commercially available triple salt (2:1:1 molar mix of KHSO5, KHSO4, and K2SO4), wherein the active oxidizing reagent is KHSO5.4 It is a white crystalline solid, which is stable and easy to handle. In addition, it is incredibly cheap, which can compete with the cost of H2O2 and bleach. More importantly, based on animal studies, it has a low order of toxicity when taken internally, and the byproducts associated with Oxone are generally recognized as safe.4a Solvents are used in large quantities in the chemical industry nowadays, which define a major part of the environmental performance of a process and also impact cost, safety, and health issues.5 Therefore, the use of less toxic solvents is encouraged. Ethanol is considered a green biosolvent because it can be produced by fermentation of sugar-containing feeds, starchy feed materials, or lignocellulosic materials, which are renewable resources.6 The synthesis of sulfur-containing compounds continues to be an active and challenging field of organic chemistry.7 In particular, β-hydroxysulfones are important structural motifs in © 2017 American Chemical Society

Received: June 8, 2017 Published: September 6, 2017 10628

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

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The Journal of Organic Chemistry

achieved in 52% yield using 2-naphthalenethiol as the substrate. However, reacting p-toluenethiol with different aryl olefins with electron-donating groups or electron-withdrawing groups at the para-, meta-, and ortho-positions of the aryl ring all provided the corresponding products in high yields (Scheme 2, 3aa−3aj). The reactions are tolerant to fluoro, chloro, and bromo substituents on the aromatic ring of styrenes and phenthiols, and the corresponding target products were obtained in good to high yields (Scheme 2, 3da−3fa, 3ae−3ai). The styrene that had a strong electron-withdrawing group such as NO2 worked smoothly to afford the corresponding product 3aj in 76% yield. Moreover, α-methylstyrene gave the corresponding tertiary βhydroxysulfone 3ak in 85% yield. To develop a more general and useful method, we shifted to investigate other alkene partners. Acrylic esters and amides were selected as the next research subjects due to their potential for the synthesis of bioactive molecules. As shown in Scheme 3, again, reacting different phenthiols bearing either electron-donating groups or electron-withdrawing groups with methyl methacrylate all gave the corresponding products in good to high yields (Scheme 3, 3am−3im), and various α,βunsaturated esters and amides were effective as substrates in this system, too (Scheme 3, 3aa−3aq). To demonstrate the practicality of this transformation, a multigram-scale reaction was performed between commercially available thiophenol 1d and α,β-unsaturated amide 2q to synthesize the anticancer drug bicalutamide.13 The corresponding pharmaceutical molecule 3dq was prepared in 68% yield (2.92 g) in a one-pot manner (Scheme 4). To have a better understanding of this transformation, intermediate B (β-hydroperoxysulfone, Scheme 5) was isolated from the reaction mixture of 1a and 2a before NaBH4 was added. The structure of intermediate B was identified by HRMS, 1H NMR, and 13C NMR spectroscopy and was confirmed using single-crystal X-ray diffraction.14 Tetramethylpiperidin-1-oxyl (TEMPO), a well-known radical scavenger, was added in the reaction of 1a with 2a. No desired product was observed in the reaction. However, 2,2,6,6-tetramethyl-1((phenylthio)oxy)-piperidine formed from the reaction of TEMPO, and the thiophenyl radical was isolated in a low yield. This result suggests that the reaction includes a radical process and is initiated by a thiyl radical, which was generated by auto-oxidation. On the basis of the above evidence and previous work,3b a tentative mechanism for this one-pot reaction of thiophenols with olefins is shown in Scheme 5. βHydroperoxysulfide intermediate A was first formed through an auto-oxidative difunctionalization reaction of 1a and 2a. Intermediate A was then oxidized by Oxone to generate βhydroperoxysulfone intermediate B. Finally, a reductive workup by NaBH4 resulted in the desired product β-hydroxysulfone 3aa. In summary, a mild transformation for the one-pot synthesis of substituted β-hydroxysulfones is described. The reaction proceeds via the formation of β-hydroperoxysulfides as versatile intermediates, which were obtained through an auto-oxidative difunctionalization reaction of alkenes and thiols. β-Hydroperoxysulfides were then transformed to β-hydroperoxysulfones using Oxone as a sustainable oxidant. β-Hydroperoxysulfones were sequentially reduced by NaBH4 to provide the desired βhydroxysulfones in high yields. All steps were carried out in a one-pot manner to provide the desired products in an efficient way. The reactions were carried out using less hazardous ethanol as a solvent under mild reaction conditions. This one-

the solvent at room temperature, followed by the addition of Oxone or mCPBA as the oxidant and then workup with NaBH4, gave the desired β-hydroxysulfone product (3aa) in excellent yield (Scheme 1, entries 1 and 2). The structure of Scheme 1. Screening of Reaction Conditionsa

a

Standard reaction conditions: 1 (0.5 mmol), 2 (0.5 mmol), O2 (balloon), Oxone (0.55 mmol), NaBH4 (0.55 mmol), EtOH (5 mL), 30 °C. bIsolated yield. cReaction time: step 1, 5 h; step 2, 12 h; step 3, 0.1 h.

3aa was confirmed using single-crystal X-ray diffraction as shown in Scheme 5.12 Treatment of styrene and p-toluenethiol with other oxidants such as K2S2O8, H2O2, and CH3CO3H provided no desired product (Scheme 1, entries 3−5). In view of the environmentally safe and benign nature of Oxone, it was chosen for the further reaction conditions screening. The reductant played a key role in the present reaction, too (Scheme 1, entries 6−11). NaBH4 was the most effective one among the tested reducing agents. Different solvents were then evaluated, and the results showed that the reaction proceeded optimally in ethanol (Scheme 1, entries 12−18). The screening of temperature suggested that 30 °C was the best choice for the transformation (Scheme 1, entries 19−21). Increasing the temperature resulted in slightly lower yields. After various reaction parameters were optimized, the best results were found under the following conditions: O2 (balloon), Oxone (1.1 equiv), and NaBH4 (1.1 equiv) at 30 °C in EtOH. Under these reaction conditions, a 97% yield of 3aa was obtained after 17 h (Scheme 1, entry 19). Having optimized conditions in hand, we pursued the exploration of the substrate scope. Phenthiols bearing either electron-donating groups or electron-withdrawing groups could furnish the desired β-hydroxysulfones in high yields (Scheme 2, 3aa−3ha), and the corresponding product 3ia could be 10629

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

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The Journal of Organic Chemistry Scheme 2. Reactions of Thiophenols 1a−i with Styrenes 2a−la,b,c

a b

Standard reaction conditions: 1 (0.5 mmol), 2 (0.5 mmol), O2 (balloon), Oxone (0.55 mmol), NaBH4 (0.55 mmol), EtOH (5 mL), 30 °C. Reaction time: step 1, 4−14 h; step 2, 12 h; step 3, 0.1−0.5 h. cIsolated yield. Characterization of the Products. 1-Phenyl-2-tosylethanol (3aa). The desired pure product was obtained in 97% yield (134.4 mg) as a white solid, mp 74−75 °C. 1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 7.33−7.25 (m, 5H), 5.24 (d, J = 10.0 Hz, 1H), 3.74 (s, 1H), 3.47 (dd, J = 14.4, 10.1 Hz, 1H), 3.31 (dd, J = 14.5, 1.7 Hz, 1H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 145.2, 140.8, 136.2, 130.1, 128.7, 128.3, 128.0, 125.7, 68.5, 64.0, 21.7. HRMS (ESI): m/z exact mass calcd for C15H16NaO3S [M + Na], 299.0718; found, 299.0712. 2-((4-Isopropylphenyl)sulfonyl)-1-phenylethanol (3ba). The desired pure product was obtained in 93% yield (141.5 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.86 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 7.34−7.24 (m, 5H), 5.28 (d, J = 10.0 Hz, 1H), 3.76 (s, 1H), 3.48 (dd, J = 14.3, 10.1 Hz, 1H), 3.34 (dd, J = 14.4, 1.6 Hz, 1H), 3.06−2.96 (m, 1H), 1.29 (d, J = 6.9 Hz, 6H). 13C NMR (151 MHz, CDCl3): δ 155.9, 140.7, 136.4, 128.7, 128.3, 128.1, 127.6, 125.7, 68.4, 64.0, 34.3, 23.6. HRMS (ESI): m/z exact mass calcd for C17H20NaO3S [M + Na], 327.1031; found, 327.1027. 2-((4-Methoxyphenyl)sulfonyl)-1-phenylethanol (3ca). The desired pure product was obtained in 77% yield (112.6 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.87 (d, J = 8.5 Hz, 2H), 7.33−

pot sequential approach should reduce the cost and waste associated with pharmaceutical synthesis.

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EXPERIMENTAL SECTION

For the one-pot synthesis of β-hydroxysulfones, thiophenols (1, 0.5 mmol) and alkenes (2, 0.5 mmol) were dissolved in ethanol (5 mL) at 30 °C. The reactions were performed under an oxygen atmosphere (balloon) until substrates disappeared. Oxone (0.55 mmol) was then added. The reactions were completed in 12 h as monitored by TLC. Thereafter, NaBH4 (0.55 mmol) was added to the reaction mixtures, which were stirred for a few minutes. The products were isolated by silica gel column chromatography using petroleum ether/ethyl acetate (v/v 10:1 to 3:1). For the gram-scale synthesis of bicalutamide, thiophenol 1d (1.63 mL) and alkene 2q (2.58 g) were dissolved in ethanol (100 mL) at 45 °C. The reaction was performed under an oxygen atmosphere (balloon) until substrates disappeared. Oxone (0.55 mmol) was then added. The reaction was completed in 28 h as monitored by TLC. The product 3dq was isolated by silica gel column chromatography using petroleum ether/ethyl acetate (v/v 4:1). 10630

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

Note

The Journal of Organic Chemistry Scheme 3. Reactions of Thiophenols 1a−i with α,β-Unsaturated Esters/Amides 2m−qa,b,c

a b

Standard reaction conditions: 1 (0.5 mmol), 2 (0.5 mmol), O2 (balloon), Oxone (0.55 mmol), NaBH4 (0.55 mmol), EtOH (5 mL), 30 °C. Reaction time: step 1, 4−17 h; step 2, 12 h; step 3, 0.1−0.5 h. cIsolated yield. dReduction step is not needed. Hz, 1H), 3.52 (dd, J = 14.5, 10.0 Hz, 1H), 3.44 (d, J = 2.3 Hz, 1H), 3.34 (dd, J = 14.5, 1.7 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 140.9, 140.5, 137.8, 129.7, 129.5, 128.8, 128.5, 125.6, 68.6, 64.0. HRMS (ESI): m/z exact mass calcd for C14H13ClNaO3S [M + Na], 319.0172; found, 319.0171. 2-((4-Bromophenyl)sulfonyl)-1-phenylethanol (3fa). The desired pure product was obtained in 80% yield (136.5 mg) as a white solid, mp 121−122 °C. 1H NMR (600 MHz, CDCl3): δ 7.81 (d, J = 8.5 Hz, 2H), 7.72 (d, J = 8.5 Hz, 2H), 7.35−7.31 (m, 2H), 7.31−7.27 (m, 3H), 5.28 (d, J = 10.0 Hz, 1H), 3.52 (dd, J = 14.5, 10.0 Hz, 1H), 3.43 (d, J = 2.2 Hz, 1H), 3.34 (dd, J = 14.5, 1.8 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 140.5, 138.4, 132.7, 129.6, 129.5, 128.8, 128.5, 125.6, 68.6, 64.0. HRMS (ESI): m/z exact mass calcd for C14H13BrNaO3S [M + Na], 362.9667; found, 362.9672. 1-Phenyl-2-(phenylsulfonyl)ethanol (3ga). The desired pure product was obtained in 74% yield (97.4 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.96 (d, J = 7.4 Hz, 2H), 7.69 (t, J = 7.5 Hz, 1H), 7.60 (t, J = 7.7 Hz, 2H), 7.36−7.26 (m, 5H), 5.28 (d, J = 10.1 Hz, 1H), 3.66 (s, 1H), 3.51 (dd, J = 14.4, 10.2 Hz, 1H), 3.35 (d, J = 14.4 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 140.6, 139.2, 134.1, 129.5, 128.8, 128.4, 128.0, 125.6, 68.5, 64.0. HRMS (ESI): m/z exact mass calcd for C14H14NaO3S [M + Na], 285.0561; found, 285.0554. 1-Phenyl-2-(m-tolylsulfonyl)ethanol (3ha). The desired pure product was obtained in 82% yield (113.3 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.77−7.73 (m, 2H), 7.50−7.44 (m, 2H), 7.34−7.25 (m, 5H), 5.27 (d, J = 10.0 Hz, 1H), 3.74 (s, 1H), 3.49 (dd, J = 14.4, 10.1 Hz, 1H), 3.34 (dd, J = 14.4, 1.6 Hz, 1H), 2.45 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 140.6, 139.8, 139.0, 134.9, 129.3, 128.7,

Scheme 4. Gram-Scale Synthesis of Bicalutamide in a OnePot Manner

7.23 (m, 5H), 7.02 (d, J = 8.9 Hz, 2H), 5.23 (d, J = 10.1 Hz, 1H), 3.88 (s, 3H), 3.77 (d, J = 2.0 Hz, 1H), 3.46 (dd, J = 14.2, 10.2 Hz, 1H), 3.30 (d, J = 14.4 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 164.0, 140.8, 130.6, 130.2, 128.7, 128.3, 125.7, 114.7, 68.5, 64.2, 55.8. HRMS (ESI): m/z exact mass calcd for C15H16NaO4S [M + Na], 315.0667; found, 315.0666. 2-((4-Fluorophenyl)sulfonyl)-1-phenylethanol (3da). The desired pure product was obtained in 81% yield (113.5 mg) as a colorless oil. 1 H NMR (600 MHz, CDCl3): δ 8.00−7.93 (m, 2H), 7.35−7.22 (m, 7H), 5.28 (d, J = 9.9 Hz, 1H), 3.54−3.49 (m, 2H), 3.34 (dd, J = 14.5, 1.4 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 166.8, 165.1, 140.6, 135.4, 131.0, 130.9, 128.8, 128.4, 125.6, 116.8, 116.7, 68.6, 64.1. HRMS (ESI): m/z exact mass calcd for C14H13FNaO3S [M + Na], 303.0467; found, 303.0470. 2-((4-Chlorophenyl)sulfonyl)-1-phenylethanol (3ea). The desired pure product was obtained in 77% yield (114.2 mg) as a white solid, mp 106−108 °C. 1H NMR (600 MHz, CDCl3): δ 7.89 (d, J = 8.6 Hz, 2H), 7.55 (d, J = 8.6 Hz, 2H), 7.35−7.27 (m, 5H), 5.28 (d, J = 10.0 10631

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

Note

The Journal of Organic Chemistry Scheme 5. Reaction Mechanism

14.4, 1.6 Hz, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 163.3, 161.7, 145.4, 136.5, 136.5, 136.1, 130.1, 128.0, 127.5, 127.4, 115.7, 115.7, 115.5, 67.9, 64.0, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15FNaO3S [M + Na], 317.0624; found, 317.0630. 1-(4-Bromophenyl)-2-tosylethanol (3af). The desired pure product was obtained in 60% yield (106.6 mg) as a white solid, mp 110− 112 °C. 1H NMR (600 MHz, CDCl3): δ 7.81 (d, J = 8.3 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 5.21 (d, J = 10.0 Hz, 1H), 3.84 (s, 1H), 3.43 (dd, J = 14.4, 10.0 Hz, 1H), 3.28 (dd, J = 14.4, 1.8 Hz, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.4, 139.7, 136.0, 131.8, 130.1, 128.0, 127.4, 122.1, 68.0, 63.8, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15BrNaO3S [M + Na], 376.9823; found, 376.9814. 1-(4-Chlorophenyl)-2-tosylethanol (3ag). The desired pure product was obtained in 79% yield (122.8 mg) as a white solid, mp 98−99 °C. 1H NMR (600 MHz, CDCl3): δ 7.82 (d, J = 8.3 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.5 Hz, 2H), 7.23 (d, J = 8.5 Hz, 2H), 5.23 (d, J = 10.0 Hz, 1H), 3.83 (s, 1H), 3.42 (dd, J = 14.4, 10.0 Hz, 1H), 3.28 (dd, J = 14.4, 1.7 Hz, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.4, 139.2, 136.0, 134.0, 130.1, 128.9, 128.0, 127.1, 67.8, 63.8, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15ClNaO3S [M + Na], 333.0328; found, 333.0336. 1-(3-Chlorophenyl)-2-tosylethanol (3ah). The desired pure product was obtained in 74% yield (115.1 mg) as a white solid, mp 102−104 °C. 1H NMR (600 MHz, CDCl3): δ 7.81 (d, J = 7.3 Hz, 2H), 7.38 (d, J = 7.7 Hz, 2H), 7.29 (s, 1H), 7.25−7.22 (m, 2H), 7.18− 7.14 (m, 1H), 5.22 (d, J = 10.0 Hz, 1H), 3.84 (s, 1H), 3.43 (dd, J = 14.4, 10.0 Hz, 1H), 3.30 (dd, J = 14.4, 1.4 Hz, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.4, 142.7, 136.0, 134.6, 130.1, 130.0, 128.4, 128.0, 125.9, 123.8, 67.9, 63.8, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15ClNaO3S [M + Na], 333.0328; found, 333.0323. 1-(2-Chlorophenyl)-2-tosylethanol (3ai). The desired pure product was obtained in 76% yield (118.0 mg) as a white solid, mp 116−118 °C. 1H NMR (600 MHz, CDCl3): δ 7.87 (d, J = 8.1 Hz, 2H), 7.67 (d, J = 7.8 Hz, 1H), 7.40 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.5 Hz, 1H), 7.26−7.20 (m, 2H), 5.42 (d, J = 10.0 Hz, 1H), 4.01 (s, 1H), 3.50 (d, J = 14.5 Hz, 1H), 3.27 (dd, J = 14.6, 10.0 Hz, 1H), 2.47 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.3, 137.8, 135.6, 130.9, 130.1, 129.4, 129.2, 128.2, 127.4, 127.2, 65.5, 61.8, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15ClNaO3S [M + Na], 333.0328; found, 333.0332. 1-(4-Nitrophenyl)-2-tosylethanol (3aj). The desired pure product was obtained in 76% yield (122.0 mg) as a white solid, mp 131−133 °C. 1H NMR (600 MHz, CDCl3): δ 8.17 (d, J = 8.8 Hz, 2H), 7.83 (d, J = 8.3 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 5.39 (d, J = 9.4 Hz, 1H), 4.04 (s, 1H), 3.43 (dd, J = 14.3, 10.0 Hz, 1H), 3.32 (dd, J = 14.3, 1.8 Hz, 1H), 2.47 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 147.7, 147.7, 145.7, 135.8, 130.3, 128.0, 126.6, 123.9, 67.7,

128.3, 128.2, 125.7, 125.1, 68.4, 63.9, 21.3. HRMS (ESI): m/z exact mass calcd for C15H16NaO3S [M + Na], 299.0718; found, 299.0723. 2-(Naphthalen-2-ylsulfonyl)-1-phenylethanol (3ia). The desired pure product was obtained in 52% yield (81.2 mg) as a white solid, mp 124−126 °C. 1H NMR (600 MHz, CDCl3): δ 8.54 (s, 1H), 8.05−7.99 (m, 2H), 7.95 (d, J = 8.1 Hz, 1H), 7.91 (dd, J = 8.6, 1.8 Hz, 1H), 7.72−7.68 (m, 1H), 7.68−7.64 (m, 1H), 7.31−7.27 (m, 4H), 7.26− 7.23 (m, 1H), 5.31 (d, J = 10.1 Hz, 1H), 3.72 (d, J = 2.0 Hz, 1H), 3.58 (dd, J = 14.5, 10.1 Hz, 1H), 3.43 (dd, J = 14.5, 1.7 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 140.6, 135.9, 135.4, 132.1, 130.0, 129.9, 129.6, 129.5, 128.7, 128.3, 128.0, 127.9, 125.6, 122.4, 68.5, 64.0. HRMS (ESI): m/z exact mass calcd for C18H16NaO3S [M + Na], 335.0718; found, 335.0723. 1-(p-Tolyl)-2-tosylethanol (3ab). The desired pure product was obtained in 95% yield (138.0 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.83 (d, J = 8.1 Hz, 2H), 7.37 (d, J = 7.9 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 5.20 (d, J = 10.1 Hz, 1H), 3.66 (s, 1H), 3.47 (dd, J = 14.4, 10.1 Hz, 1H), 3.30 (dd, J = 14.4, 1.4 Hz, 1H), 2.46 (s, 3H), 2.31 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.2, 138.1, 137.8, 136.2, 130.1, 129.4, 128.0, 125.6, 68.3, 64.0, 21.7, 21.1. HRMS (ESI): m/z exact mass calcd for C16H18NaO3S [M + Na], 313.0874; found, 313.0867. 1-(4-(tert-Butyl)phenyl)-2-tosylethanol (3ac). The desired pure product was obtained in 94% yield (156.3 mg) as a white solid, mp 108−110 °C. 1H NMR (600 MHz, CDCl3): δ 7.82 (d, J = 8.2 Hz, 2H), 7.37 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 5.23 (d, J = 10.0 Hz, 1H), 3.66 (s, 1H), 3.50 (dd, J = 14.5, 1.8 Hz, 1H), 3.34 (dd, J = 14.5, 1.8 Hz, 1H), 2.46 (s, 3H), 1.28 (s, 9H). 13 C NMR (151 MHz, CDCl3): δ 151.3, 145.1, 137.8, 137.7, 136.3, 130.0, 128.0, 125.6, 125.4, 68.3, 63.9, 34.5, 31.3, 21.7. HRMS (ESI): m/z exact mass calcd for C19H24NaO3S [M + Na], 355.1344; found, 355.1338. 1-(4-Methoxyphenyl)-2-tosylethanol (3ad). The desired pure product was obtained in 70% yield (107.2 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.82 (d, J = 7.4 Hz, 2H), 7.37 (d, J = 7.8 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 6.83 (d, J = 7.9 Hz, 2H), 5.19 (d, J = 10.0 Hz, 1H), 3.76 (s, 3H), 3.67 (s, 1H), 3.47 (dd, J = 14.4, 10.1 Hz, 1H), 3.29 (dd, J = 14.4, 1.6 Hz, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 159.5, 145.2, 136.2, 132.9, 130.1, 128.0, 127.0, 114.1, 68.1, 64.0, 55.3, 21.7. HRMS (ESI): m/z exact mass calcd for C16H18NaO4S [M + Na], 329.0824; found, 329.0828. 1-(4-Fluorophenyl)-2-tosylethanol (3ae). The desired pure product was obtained in 80% yield (117.7 mg) as a white solid, mp 93−95 °C. 1H NMR (600 MHz, CDCl3): δ 7.84−7.81 (m, 2H), 7.38 (d, J = 7.6 Hz, 2H), 7.29−7.24 (m, 2H), 7.02−6.96 (m, 2H), 5.24 (d, J = 10.1 Hz, 1H), 3.82 (s, 1H), 3.44 (dd, J = 14.4, 10.1 Hz, 1H), 3.28 (dd, J = 10632

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

Note

The Journal of Organic Chemistry

Methyl 2-Hydroxy-2-methyl-3-(phenylsulfonyl)propanoate (3gm). The desired pure product was obtained in 67% yield (86.5 mg) as a white solid, mp 72−76 °C. 1H NMR (400 MHz, CDCl3): δ 7.92−7.85 (m, 2H), 7.67−7.61 (m, 1H), 7.58−7.52 (m, 2H), 3.80− 3.73 (m, 5H), 3.55 (d, J = 14.7 Hz, 1H), 1.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.3, 140.5, 133.8, 129.1, 128.0, 72.3, 63.8, 53.4, 27.2. HRMS (ESI): m/z exact mass calcd for C11H14NaO5S [M + Na], 281.0460; found, 281.0464. Methyl 2-Hydroxy-2-methyl-3-(m-tolylsulfonyl)propanoate (3hm). The desired pure product was obtained in 85% yield (115.7 mg) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.72−7.68 (m, 2H), 7.46−7.41 (m, 2H), 3.79 (s, 3H), 3.78 (s, 1H), 3.75 (d, J = 14.6 Hz, 1H), 3.54 (d, J = 14.6 Hz, 1H), 2.45 (s, 3H), 1.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.3, 140.4, 139.4, 134.6, 129.0, 128.3, 125.1, 72.3, 63.8, 53.3, 27.2, 21.3. HRMS (ESI): m/z exact mass calcd for C12H16NaO5S [M + Na], 295.0616; found, 295.0607. Methyl 2-Hydroxy-2-methyl-3-(naphthalen-2-ylsulfonyl)propanoate (3im). The desired pure product was obtained in 47% yield (72.5 mg) as a white solid, mp 102−104 °C. 1H NMR (600 MHz, CDCl3): δ 8.46 (s, 1H), 7.99 (d, J = 8.5 Hz, 2H), 7.92 (d, J = 8.2 Hz, 1H), 7.86 (dd, J = 8.6, 1.8 Hz, 1H), 7.69−7.65 (m, 1H), 7.64− 7.61 (m,1H), 3.83 (d, J = 14.7 Hz, 1H), 3.79 (s, 1H), 3.76 (s, 3H), 3.63 (d, J = 14.7 Hz, 1H), 1.46 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 174.4, 137.3, 135.3, 132.0, 129.9, 129.5, 129.4, 129.4, 128.0, 127.7, 122.6, 72.4, 63.8, 53.4, 27.2. HRMS (ESI): m/z exact mass calcd for C15H16NaO5S [M + Na], 331.0616; found, 331.0624. Allyl 2-Hydroxy-2-methyl-3-tosylpropanoate (3an). The desired pure product was obtained in 86% yield (128.3 mg) as a colorless oil. 1 H NMR (600 MHz, CDCl3): δ 7.76 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 5.97−5.90 (m, 1H), 5.35 (dd, J = 17.2, 1.3 Hz, 1H), 5.28 (dd, J = 10.4, 1.0 Hz, 1H), 4.71 (dd, J = 12.9, 6.0 Hz, 1H), 4.60 (dd, J = 12.9, 5.8 Hz, 1H), 3.78 (s, 1H), 3.75 (d, J = 14.6 Hz, 1H), 3.53 (d, J = 14.6 Hz, 1H), 2.43 (s, 3H), 1.45 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 173.7, 144.8, 137.7, 131.3, 129.7, 128.1, 119.3, 72.4, 67.2, 63.9, 27.2, 21.6. HRMS (ESI): m/z exact mass calcd for C14H18NaO5S [M + Na], 321.0773; found, 321.0778. 2-Hydroxyethyl 2-Hydroxy-2-methyl-3-tosylpropanoate (3ao). The desired pure product was obtained in 64% yield (96.7 mg) as a colorless oil. 1H NMR (600 MHz, CDCl3): δ 7.76 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 4.59−4.53 (m, 1H), 4.24 (ddd, J = 11.5, 6.8, 2.5 Hz, 1H), 3.95 (ddd, J = 13.0, 6.8, 2.3 Hz, 1H), 3.85 (ddd, J = 13.1, 5.8, 2.5 Hz, 1H), 3.80 (d, J = 14.6 Hz, 1H), 3.55 (d, J = 14.6 Hz, 1H), 3.06 (s, 1H), 2.42 (s, 3H), 1.45 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 174.2, 145.1, 137.4, 129.8, 128.0, 72.5, 68.6, 64.1, 60.5, 27.5, 21.6. HRMS (ESI): m/z exact mass calcd for C13H18NaO6S [M + Na], 325.0722; found, 325.0720. 2-Hydroxy-2-methyl-N-phenyl-3-tosylpropanamide (3ap). The desired pure product was obtained in 78% yield (130.0 mg) as a white solid, mp 155−157 °C. 1H NMR (600 MHz, CDCl3): δ 8.68 (s, 1H), 7.72 (d, J = 8.3 Hz, 2H), 7.39−7.35 (m, 2H), 7.29 (t, J = 7.9 Hz, 2H), 7.19 (d, J = 8.1 Hz, 2H), 7.13−7.09 (t, J = 7.4 Hz, 1H), 5.17 (s, 1H), 3.99 (d, J = 14.6 Hz, 1H), 3.46 (d, J = 14.6 Hz, 1H), 2.33 (s, 3H), 1.58 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 170.2, 145.5, 137.0, 135.8, 129.9, 128.9, 128.0, 124.5, 119.5, 74.0, 61.4, 27.8, 21.6. HRMS (ESI): m/z exact mass calcd for C17H19NNaO4S [M + Na], 356.0933; found, 356.0936. N-(4-Cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-tosylpropanamide (3aq). The desired pure product was obtained in 70% yield (149.2 mg) as a white solid, mp 179−181 °C. 1H NMR (600 MHz, DMSO-d6): δ 10.33 (s, 1H), 8.41 (s, 1H), 8.18 (d, J = 8.6 Hz, 1H), 8.06 (d, J = 8.6 Hz, 1H), 7.71 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 6.38 (s, 1H), 3.89 (d, J = 14.7 Hz, 1H), 3.63 (d, J = 14.8 Hz, 1H), 2.25 (s, 3H), 1.39 (s, 3H). 13C NMR (151 MHz, DMSO-d6): δ 173.7, 143.9, 143.2, 137.8, 136.1, 135.8, 131.5, 131.2, 131.0, 129.3, 128.1, 125.2, 123.4, 122.8, 121.6, 119.8, 117.5, 117.4, 115.8, 101.8, 73.1, 63.5, 27.2, 20.9. HRMS (ESI): m/z exact mass calcd for C19H17F3N2NaO4S [M + Na], 449.0759; found, 449.0765. N-(4-Cyano-3-(trifluoromethyl)phenyl)-3-((4-fluorophenyl)sulfonyl)-2-hydroxy-2-methylpropanamide (3dq). The desired pure product was obtained in 74% yield (159.2 mg) as a white solid, mp

63.6, 21.7. HRMS (ESI): m/z exact mass calcd for C15H15NNaO5S [M + Na], 344.0569; found, 344.0577. 2-Phenyl-1-tosylpropan-2-ol (3ak). The desired pure product was obtained in 85% yield (123.4 mg) as a white solid, mp 83−85 °C. 1H NMR (600 MHz, CDCl3): δ 7.48 (d, J = 8.2 Hz, 2H), 7.30−7.27 (m, 2H), 7.21−7.13 (m, 5H), 4.63 (s, 1H), 3.69 (d, J = 14.7 Hz, 1H), 3.59 (d, J = 14.7 Hz, 1H), 2.38 (s, 3H), 1.70 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 144.5, 137.4, 129.7, 128.2, 127.5, 127.1, 124.6, 73.1, 66.7, 30.7, 21.5. HRMS (ESI): m/z exact mass calcd for C16H18NaO3S [M + Na], 313.0874; found, 313.0869. 2-Tosyl-2,3-dihydro-1H-inden-1-ol (3al). The desired pure product was obtained in 90% yield (130.0 mg) as a white solid, mp 138−140 °C. 1H NMR (600 MHz, CDCl3): δ 7.87 (d, J = 8.2 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 7.39−7.36 (m, 1H), 7.28−7.24 (m, 3H), 7.15 (d, J = 6.5 Hz, 2H), 5.79−5.75 (m, 1H), 3.87−3.82 (m, 1H), 3.28 (dd, J = 15.9, 9.3 Hz, 1H), 3.13 (dd, J = 15.9, 8.8 Hz, 1H), 2.75 (d, J = 4.7 Hz, 1H), 2.47 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.2, 141.2, 137.7, 135.3, 130.1, 129.0, 128.5, 127.7, 124.5, 124.4, 75.5, 72.9, 31.7, 21.7. HRMS (ESI): m/z exact mass calcd for C16H16NaO3S [M + Na], 311.0718; found, 311.0723. Methyl 2-Hydroxy-2-methyl-3-tosylpropanoate (3am). The desired pure product was obtained in 75% yield (101.5 mg) as a white solid, mp 65−67 °C. 1H NMR (600 MHz, CDCl3): δ 7.76 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 3.78 (s, 3H), 3.76 (s, 1H), 3.73 (d, J = 14.6 Hz, 1H), 3.52 (d, J = 14.6 Hz, 1H), 2.43 (s, 3H), 1.44 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ 174.4, 144.8, 137.6, 129.7, 128.1, 72.3, 63.9, 53.3, 27.2, 21.6. HRMS (ESI): m/z exact mass calcd for C12H16NaO5S [M + Na], 295.0616; found, 295.0609. Methyl 2-Hydroxy-3-((4-isopropylphenyl)sulfonyl)-2-methylpropanoate (3bm). The desired pure product was obtained in 90% yield (135.2 mg) as a white solid, mp 83−84 °C. 1H NMR (600 MHz, CDCl3): δ 7.80 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.3 Hz, 2H), 3.80 (s, 1H), 3.77 (s, 3H), 3.74 (d, J = 14.6 Hz, 1H), 3.53 (d, J = 14.6 Hz, 1H), 3.03−2.95 (m, 1H), 1.45 (s, 3H), 1.27 (d, J = 6.9 Hz, 6H). 13C NMR (151 MHz, CDCl3): δ 174.3, 155.5, 137.8, 128.2, 127.3, 72.3, 63.9, 53.3, 34.3, 27.2, 23.6. HRMS (ESI): m/z exact mass calcd for C14H20NaO5S [M + Na], 323.0929; found, 323.0937. Methyl 2-Hydroxy-3-((4-methoxyphenyl)sulfonyl)-2-methylpropanoate (3cm). The desired pure product was obtained in 60% yield (86.5 mg) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.83−7.79 (m, 2H), 7.02−6.98 (m, 2H), 3.88 (s, 3H), 3.79 (s, 3H), 3.77 (s, 1H), 3.73 (d, J = 14.7 Hz, 1H), 3.50 (d, J = 14.6 Hz, 1H), 1.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.4, 163.8, 132.0, 130.3, 114.3, 72.4, 64.0, 55.7, 53.3, 27.2. HRMS (ESI): m/z exact mass calcd for C12H16NaO6S [M + Na], 311.0565; found, 311.0558. Methyl 3-((4-Fluorophenyl)sulfonyl)-2-hydroxy-2-methylpropanoate (3dm). The desired pure product was obtained in 80% yield (110.5 mg) as a white solid, mp 65−67 °C. 1H NMR (400 MHz, CDCl3): δ 7.94−7.88 (m, 2H), 7.24−7.18 (m, 2H), 3.83 (s, 3H), 3.76 (d, J = 14.7 Hz, 1H), 3.66 (s, 1H), 3.55 (d, J = 14.8 Hz, 1H), 1.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.5, 166.7, 165.0, 136.7, 136.7, 131.1, 131.1, 116.4, 116.3, 72.3, 63.9, 53.5, 27.3. HRMS (ESI): m/z exact mass calcd for C11H13FNaO5S [M + Na], 299.0365; found, 299.0375. Methyl 3-((4-Chlorophenyl)sulfonyl)-2-hydroxy-2-methylpropanoate (3em). The desired pure product was obtained in 78% yield (114.0 mg) as a white solid, mp 106−108 °C. 1H NMR (400 MHz, CDCl3): δ 7.86−7.82 (m, 2H), 7.55−7.50 (m, 2H), 3.85 (s, 3H), 3.77 (d, J = 14.8 Hz, 1H), 3.63 (s, 1H), 3.56 (d, J = 14.8 Hz, 1H), 1.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.5, 140.5, 139.1, 129.7, 129.4, 72.3, 63.8, 53.5, 27.3. HRMS (ESI): m/z exact mass calcd for C11H13ClNaO5S [M + Na], 315.0070; found, 315.0069. Methyl 3-((4-Bromophenyl)sulfonyl)-2-hydroxy-2-methylpropanoate (3fm). The desired pure product was obtained in 81% yield (136.6 mg) as a white solid, mp 118−120 °C. 1H NMR (400 MHz, CDCl3): δ 7.78−7.74 (m, 2H), 7.71−7.68 (m, 2H), 3.84 (s, 3H), 3.76 (d, J = 14.7 Hz, 1H), 3.62 (s, 1H), 3.55 (d, J = 14.8 Hz, 1H), 1.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 174.5, 139.7, 132.4, 129.7, 129.1, 72.3, 63.8, 53.5, 27.3. HRMS (ESI): m/z exact mass calcd for C11H13BrNaO5S [M + Na], 358.9565; found, 358.9558. 10633

DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634

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The Journal of Organic Chemistry 191−192 °C. 1H NMR (600 MHz, DMSO-d6): δ 10.36 (s, 1H), 8.42 (s, 1H), 8.21 (d, J = 8.6 Hz, 1H), 8.06 (d, J = 8.6 Hz, 1H), 7.94−7.90 (m, 2H), 7.37−7.32 (m, 2H), 6.39 (s, 1H), 3.94 (d, J = 14.9 Hz, 1H), 3.70 (d, J = 14.9 Hz, 1H), 1.40 (s, 3H). 13C NMR (151 MHz, DMSOd6): δ 173.7, 165.7, 164.0, 143.1, 137.1, 137.1, 136.2, 131.8, 131.5, 131.3, 131.1, 125.2, 123.4, 122.9, 122.8, 121.6, 119.8, 117.6, 116.1, 115.9, 115.8, 102.0, 73.1, 63.5, 27.2. HRMS (ESI): m/z exact mass calcd for C18H14F4N2NaO4S [M + Na], 453.0508; found, 453.0501. 1-((2-Hydroperoxy-2-phenylethyl)sulfonyl)-4-methylbenzene (Intermediate B). 1H NMR (600 MHz, CDCl3): δ 8.79 (s, 1H), 7.79 (d, J = 8.0 Hz, 2H), 7.35−7.25 (m, 7H), 5.43 (dd, J = 8.7, 3.9 Hz, 1H), 3.86 (dd, J = 14.8, 8.9 Hz, 1H), 3.45 (dd, J = 14.7, 4.0 Hz, 1H), 2.43 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.0, 137.1, 136.3, 129.9, 129.0, 128.8, 128.2, 127.0, 81.5, 59.5, 21.6. HRMS (ESI): m/z exact mass calcd for C15H16NaO4S [M + Na], 315.0667; found, 315.0664.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b01371. NMR spectra of the products and ORTEP drawings of the compound 3aa and intermediate B (PDF) Crystallographic data for 3aa (CIF) Crystallographic data for intermediate B (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Congde Huo: 0000-0002-3374-7931 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (21562037) and the Fok Ying Tong Education Foundation (141116) for financially supporting this work.

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REFERENCES

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DOI: 10.1021/acs.joc.7b01371 J. Org. Chem. 2017, 82, 10628−10634