Preparation and Use of (γ,γ-Dioxyallyl)boronates

Soshi Nishino; Yuji Nishii; Koji Hirano

doi:10.1055/a-2051-1054

Synlett, Table of Contents

Synlett 2023; 34(18): 2205-2209
DOI: 10.1055/a-2051-1054

cluster

Modern Boron Chemistry: 60 Years of the Matteson Reaction

Preparation and Use of (γ,γ-Dioxyallyl)boronates

Soshi Nishino

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

,

Yuji Nishii

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

,

Koji Hirano ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

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Abstract

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Abstract

A copper-catalyzed stereoselective 1,4-acylboration of α,β-unsaturated esters with B₂pin₂ and pivalic anhydride has been developed to afford the corresponding (E)-allylboronates with two distinct oxygenated functionalities at the γ positions, which are difficult to prepare by other means. The chemoselective post functionalizations of Bpin and pivalate moieties in the product are also demonstrated.

Key words

allylboronate - borylation - conjugate addition - copper - stereoselectivity

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References

References and Notes

1a Pelter A, Smith K, Brown HC. Borane Reagents . Academic Press; London: 1988
1b Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
1c Davison M, Hughes AK, Marder TB, Wade K. Contemporary Boron Chemistry . The Royal Society of Chemistry; Cambridge: 2000
1d Boronic Acids, 2nd ed. Hall DG. Wiley-VCH; Weinheim: 2011
1e Huo H.-H, Duvall JR, Huang M.-Y, Hong R. Org. Chem. Front. 2014; 1: 303
1f Diner C, Szabó KJ. J. Am. Chem. Soc. 2017; 139: 2
1g Clement H, Hall DG. Recent Advances in the Stereoselective Additions of Allylic Boronates to Carbonyl Compounds. In Patai’s Chemistry of Functional Groups. John Wiley & Sons; Hoboken: 2020.

2a Hoffmann RW, Kemper B. Tetrahedron Lett. 1981; 22: 5263
2b Wuts PG. M, Bigelow SS. J. Org. Chem. 1982; 47: 2498
2c Brown HC, Jadhav PK, Bhat KS. J. Am. Chem. Soc. 1988; 110: 1535
2d Muñoz-Hernández L, Soderquist JA. Org. Lett. 2009; 11: 2571

3a Moriya T, Suzuki A, Miyaura N. Tetrahedron Lett. 1995; 36: 1887
3b Yamamoto Y, Miyairi T, Ohmura T, Miyaura N. J. Org. Chem. 1999; 64: 296

Hall also reported the related palladium-catalyzed olefin isomerization and consecutive allylic borylation of alkenyl triflates:

3c Lessard S, Peng F, Hall DG. J. Am. Chem. Soc. 2009; 131: 9612

4 Gao X, Hall DG. J. Am. Chem. Soc. 2003; 125: 9308

5a Yamamoto Y, Takenouchi Y, Ozaki T, Miya T, Ito H. J. Am. Chem. Soc. 2014; 136: 16515
5b Takenouchi Y, Kojima R, Momma R, Ito H. Synlett 2017; 28: 270

6 Nishino S, Hirano K. Asian J. Org. Chem. 2023; 12: e202200636
7 In the case with (i-PrCO)₂O, the Piv group derived from CsOPiv was also incorporated into the product, and the Piv-derived 1,4-acylboration product was also detected in ca. 5% ¹H NMR yield. We also tried the reaction with a 1:1 mixture of Piv₂O and Ac₂O. The corresponding Piv- and Ac-derived 1,4-acylboration products were formed in 21% and 2%, yields, respectively. Additionally, the protoboration byproduct 3a was also detected in 40% yield. Given that 3a mainly arose from the Ac-derived 1,4-acylboration product via in situ hydrolysis, the electrophilic trapping ability of Ac₂O is higher than that of Piv₂O.
8 We also monitored the reaction progress of 1k in toluene-d ₈ by ¹H NMR spectroscopy, but 2k′ was the primary product under the catalytic conditions: any acyl migration from 2k to 2k′ was not observed. See the Supporting Information for details and a related paper: Zeng L, Lai Z, Cui S. J. Org. Chem. 2018; 83: 14834

For pioneering work, see:

9a Ito H, Yamanaka H, Tateiwa J, Hosomi A. Tetrahedron Lett. 2000; 41: 6821
9b Takahashi K, Ishiyama T, Miyaura N. Chem. Lett. 2000; 29: 982

For recent reviews, see:

9c Semba K, Fujihara T, Terao J, Tsuji Y. Tetrahedron 2015; 71: 2183
9d Hemming D, Fritzemeier R, Westcott SA, Santos WL, Steel PG. Chem. Soc. Rev. 2018; 47: 7477
9e Xue W, Oestreich M. ACS Cent. Sci. 2020; 6: 1070
9f Fujihara T. Asian J. Org. Chem. 2022; 11: e202200535
9g Das KK, Mahato S, Hazra S, Panda S. Chem. Rec. 2022; 22: e202100290

10a Whiting A. Tetrahedron Lett. 1991; 32: 1503
10b Mears RJ, Whiting A. Tetrahedron 1993; 49: 177
10c Conole G, Mears RJ, De Silva H, Whiting A. J. Chem. Soc., Perkin Trans. 1 1995; 1825
10d Mears RJ, Sailes HE, Watts JP, Whiting A. J. Chem. Soc., Perkin Trans. 1 2000; 3250
10e Sailes HE, Watts JP, Whiting A. J. Chem. Soc., Perkin Trans. 1 2000; 3362
10f Zhan M, Ding Z, Du S, Chen H, Feng C, Xu M, Liu Z, Zhang M, Wu C, Lan Y, Li P. Nat. Commun. 2020; 11: 792
10g Zuo Y.-J, Chang X.-T, Hao Z.-M, Zhong C.-M. Org. Biomol. Chem. 2017; 15: 6323
10h Zuo Y.-J, Zhong Z, Fan Y, Li X, Chen X, Chang Y, Song R, Fu X, Zhang A, Zhong C.-M. Org. Biomol. Chem. 2018; 16: 9237
10i Bi Y.-P, Wang H.-M, Qu H.-Y, Liang X.-C, Zhou Y, Li X.-Y, Xu D, Shen M.-H, Xu H.-D. Org. Biomol. Chem. 2019; 17: 1542
10j Larin EM, Loup J, Polishchuk I, Ross RJ, Whyte A, Lautens M. Chem. Sci. 2020; 11: 5716
10k Nishino S, Nishii Y, Hirano K. Chem. Sci. 2022; 13: 14387

11 McElavin SM. Chem. Rev. 1949; 45: 453
12 Matteson DS. Chem. Rev. 1989; 89: 1535
13 Yin J, Bai Y, Mao M, Zhu G. J. Org. Chem. 2014; 79: 9179
14 Experimental Procedures and Characterization Data Synthesis of 2a (Scheme [4, 0].25 mmol scale) Cu(OAc)₂ (4.5 mg, 0.025 mmol), P(3,5-(CF₃)₂C₆H₃)₃ (33.5 mg, 0.050 mmol), and KOPiv (105.2 mg, 0.75 mmol) were placed in a 20 mL Schlenk tube, which was filled with nitrogen by using the Schlenk technique. CPME (1.0 mL) was then added to the tube, and the suspension was stirred for 15 min at ambient temperature. Bis(pinacolato)diboron (158.7 mg, 0.63 mmol) was then added in one portion, and the resulting solution was stirred at the same temperature. After 5 min, pivalic anhydride (69.8 mg, 0.38 mmol) and methyl (E)-5-phenylpent-2-enoate (1a, 40.5 mg, 0.25 mmol) were added dropwise. The reaction solution was stirred at room temperature for additional 18 h. The resulting mixture was directly filtered through a short pad of neutral alumina and Na₂SO₄. The filtrate was evaporated in vacuo and purified by silica gel column chromatography on neutral silica gel with hexane/ethyl acetate (20/1 → 10/1, v/v) and GPC (CHCl₃) to give 1-methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate (2a, 82.5 mg, 0.21 mmol) in 82% yield with >99:1 E/Z ratio. (E)-1-Methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate ((E)-2a) 82.5 mg (82%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.27–7.23 (m, 2 H), 7.21–7.19 (m, 2 H), 7.15 (t, J = 7.1 Hz, 1 H), 4.34 (d, J = 9.9 Hz, 1 H), 3.55 (s, 3 H), 2.74 (ddd, J = 13.6, 10.5, 5.4 Hz, 1 H), 2.59 (ddd, J = 13.6, 10.4, 6.0 Hz, 1 H), 2.09–2.03 (m, 1 H), 1.89–1.80 (m, 1 H), 1.73–1.65 (m, 1 H), 1.28 (s, 9 H), 1.25 (s, 12 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 176.5, 150.6, 142.9, 128.7, 128.3, 125.6, 98.2, 83.3, 57.1, 39.1, 35.4, 33.4, 27.2, 24.9, 24.8, 20.5 (br). ¹¹B NMR (128 MHz, CDCl₃,): δ = 32.7. HRMS (APCI): m/z [M + H]⁺ calcd for C₂₃H₃₆BO₅: 403.2654; found: 403.2666.
15 We preliminarily tested several reported conditions, including simple heating, Sc(OTf)₃ catalyst, and ZnBr₂ catalyst, for the allylation of benzaldehyde with 2a, 6, and 7. However, the allylic boronates just decomposed, and the corresponding homoallylic alcohols were not detected at all. Additional investigations are still necessary.
16 We preliminarily tried enantioselective conditions using several chiral phosphine ligands. However, the maximum enantiomeric ratio was 75:25 with a phosphoramidite ligand. See the Supporting Information for more details.

Supplementary Material

Supporting Information