Brønsted Acids of Anionic Chiral Cobalt(III) Complexes as Catalysts for the Iodoglycosylation or Iodocarboxylation of Glycals

^◊ These authors contributed equally to this work.

Abstract

Brønsted acids of anionic chiral Co(III) complexes were found to act as efficient phase-transfer catalysts for the diastereoselective iodoglycosylation or iodocarboxylation of glycals with a variety of alcohols or carboxylic acids, respectively, with N-iodosuccinimide as the iodo cation source. The corresponding 2-deoxy-2-iodoglycosides, including monosaccharides and disaccharides, and 2-deoxy-2-iodoglycosyl carboxylates, which are of high synthetic and biological importance, were obtained in high yields (up to 88%) with good diastereoselectivities (up to 9:1 dr).

Key words

Brønsted acids - phase-transfer catalysis - iodoglycosylation - iodocarboxylation - glycals

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• 15 2-Deoxy-2-Iodoglycoside 4aa; Typical Procedure A 10-mL oven-dried vial was charged with catalyst Λ-1c (7.2 mg, 0.01 mmol), NIS (24.8 mg, 0.11 mmol), activated 4 Å MS (100 mg), glycal 2a (41.6 mg, 0.10 mmol), and distilled CH₂Cl₂ (1 mL) at r.t. in the absence of light. Alcohol 3a (0.12 mmol) was added and the resulting solution was stirred vigorously under N₂ for 24 h. The reaction was then quenched with Et₃N (140 μL, 1.0 mmol) and sat. aq Na₂S₂O₃ (0.2 mL). The mixture was purified by flash column chromatography to give the 2-deoxy-2-iodoglycosides 4aa as an α/β mixture. 4aaα Colorless oil; yield: 43.9 mg (67%); R_f = 0.43 (PE–EtOAc, 10:1); [α]_D ²⁰ +3.45 (c 1.27, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 7.48–7.35 (m, 4 H), 7.35–7.19 (m, 14 H), 7.16 (d, J = 6.2 Hz, 2 H), 5.30 (s, 1 H), 4.84 (d, J = 10.8 Hz, 1 H), 4.72–4.66 (m, 3 H), 4.52–4.46 (m, 5 H), 3.92–3.91 (m, 2 H), 3.80–3.75 (m, 1 H), 3.69 (d, J = 10.8 Hz, 1 H), 3.37–3.34 (m, 1 H). ¹³C NMR (151 MHz, CDCl₃): δ = 138.46, 138.29, 137.80, 136.98, 128.51, 128.44, 128.35, 128.10, 128.08, 128.05, 127.82, 127.69, 127.52, 100.85, 100.80, 76.05, 75.31, 73.47, 72.51, 71.04, 69.54, 69.00, 33.58, 33.55. HRMS (ESI): m/z [M + Na]⁺ calcd for C₃₄H₃₅NaIO₅: 673.1427; found: 673.1420. 4aaβ White solid; yield: 9.5 mg (15%); mp 101–103 °C; R_f = 0.38 (PE–EtOAc, 10:1); [α]_D ²⁰ +4.91 (c 0.55, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 7.47–7.36 (m, 4 H), 7.36–7.26 (m, 14 H), 7.19 (d, J = 6.9 Hz, 2 H), 4.97 (d, J = 10.2 Hz, 1 H), 4.92 (d, J = 11.7 Hz, 1 H), 4.85 (d, J = 10.1 Hz, 1 H), 4.80 (d, J = 10.9 Hz, 1 H), 4.68 (d, J = 11.8 Hz, 1 H), 4.62 (t, J = 9.6 Hz, 2 H), 4.57 (t, J = 12.5 Hz, 2 H), 4.01–3.94 (m, 1 H), 3.77–3.70 (m, 3 H), 3.64 (t, J = 9.2 Hz, 1 H), 3.49 (d, J = 7.6 Hz, 1 H). ¹³C NMR (151 MHz, CDCl₃): δ = 138.17, 137.90, 137.85, 136.88, 128.55, 128.48, 128.42, 128.33, 128.18, 127.98, 127.89, 127.83, 127.76, 101.98, 86.01, 79.79, 75.62, 75.42, 75.03, 73.65, 71.39, 68.72, 32.68. HRMS (ESI): m/z [M + Na]⁺ calcd for C₃₄H₃₅NaIO₅: 673.1427; found: 673.1422. (see Supporting Information for further information).
• 16 Iodoglycosylations of either glucal (2b) or galactal (2d) with alcohol 3c in the absence of the chiral-Co^III-complex-templated Brønsted acid were also tested, affording the desired 2-deoxy-2-iodoglycosides in yields of 52% and 24% with 2.5:1 and 1.8:1 dr, respectively.
• 17 2-Deoxy-2-Iodoglycosyl Carboxylate 6a; Typical Procedure A 10-mL oven-dried vial was charged with catalyst Λ-1c (7.2 mg, 0.01 mmol), NIS (27.0 mg, 0.12 mmol), activated 4 Å MS (100 mg), glycal 2a (41.6 mg, 0.10 mmol), and distilled CH₂Cl₂ (1 mL) at r.t. in the absence of light. BzOH (5a; 0.15 mmol) was added and the resulting solution was stirred vigorously under N₂ for 12 h. The reaction was then quenched with Et₃N (140 μL, 1.0 mmol) and sat. aq Na₂S₂O₃ (0.2 mL). The mixture was purified by flash column chromatography to give the glycosyl carboxylate 6a as a α/β mixture. 6aα Colorless oil; yield: 42.7 mg (64%); R_f = 0.4 (PE–EtOAc, 8:1); [α]_D ²⁰ +3.78 (c 0.82, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 7.93 (d, J = 7.0 Hz, 2 H), 7.59 (t, J = 7.4 Hz, 1 H), 7.43 (t, J = 7.8 Hz, 2 H), 7.41–7.35 (m, 4 H), 7.34–7.24 (m, 9 H), 7.22–7.16 (m, 2 H), 6.66 (s, 1 H), 4.90 (d, J = 10.5 Hz, 1 H), 4.76–4.72 (m, 2 H), 4.58–4.52 (m, 4 H), 4.13–4.09 (m, 1 H), 4.07–4.03 (m, 1 H), 3.83 (dd, J = 11.3, 4.0 Hz, 1 H), 3.71 (dd, J = 11.3, 1.6 Hz, 1 H), 3.33 (dd, J = 8.7, 4.1 Hz, 1 H). ¹³C NMR (151 MHz, CDCl₃): δ = 164.07, 138.37, 138.08, 137.26, 133.75, 129.92, 129.12, 128.62, 128.57, 128.49, 128.38, 128.34, 128.32, 128.11, 127.94, 127.81, 127.59, 96.17, 76.20, 75.63, 75.31, 73.67, 71.22, 68.65, 31.20. HRMS (ESI): m/z [M+Na]⁺ calcd for C₃₄H₃₃INaO₆: 687.1220; found: 687.1215. 6aβ Colorless oil; yield: 6.5 mg (10%); R_f = 0.4 (PE–EtOAc, 8:1); [α]_D ²⁰ +65.61 (c 0.22, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 8.11 (d, J = 7.7 Hz, 2 H), 7.60 (t, J = 7.3 Hz, 1 H), 7.47 (t, J = 7.7 Hz, 2 H), 7.43 (d, J = 7.4 Hz, 2 H), 7.36 (t, J = 7.3 Hz, 2 H), 7.34–7.23 (m, 9 H), 7.17 (d, J = 7.4 Hz, 2 H), 6.05 (d, J = 9.5 Hz, 1 H), 5.00 (d, J = 10.2 Hz, 1 H), 4.91 (d, J = 10.2 Hz, 1 H), 4.82 (d, J = 10.8 Hz, 1 H), 4.60 (dd, J = 15.7, 11.5 Hz, 2 H), 4.48 (d, J = 12.1 Hz, 1 H), 4.19 (t, J = 9.8 Hz, 1 H), 3.87–3.69 (m, 5 H). ¹³C NMR (151 MHz, CDCl₃): δ = 164.67, 137.76, 133.75, 130.34, 128.56, 128.51, 128.45, 128.16, 128.01, 127.98, 127.86, 127.80, 95.09, 85.65, 79.07, 76.17, 75.76, 75.10, 73.71, 68.02, 30.23. HRMS (ESI): m/z [M+Na]⁺ calcd for C₃₄H₃₃INaO₆: 687.1220; found: 687.1217. (See Supporting Information for further information).