An Exploratory Study of the Enzymatic Hydroxycinnamoylation of Sucrose and Its Derivatives
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and General Remarks on the Selection of Acceptors and Donors
2.2. Free Sucrose as an Acceptor in Enzymatic Feruloylation
2.3. Enzymatic Hydroxycinnamoylation of 2,1′:4,6-Di-O-isopropylidene Sucrose 2
2.4. Enzymatic Hydroxycinnamoylation of 4,6-O-isopropylidene Sucrose 3
2.5. Enzymatic Cinnamoylation of 3′-O-acylated Sucroses 4a and 4b
3. Materials and Methods
3.1. General
3.2. Feruloylation of Free Sucrose Using Lipozyme TL IM
- 3,6-Di-O-feruloyl-α-d-glucopyranose (7bα); 2,6-di-O-feruloyl-α-d-glucopyranose (7aα); 3,6-di-O-feruloyl-β-d-glucopyranose (7bβ); 2,6-di-O-feruloyl-β-d-glucopyranose (7aβ) (3.6:2.4:2:1), Rf = 0.63 (CHCl3:MeOH–3:1). 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.9 Hz, H-A), 7.68 (d, J = 15.9 Hz, H-A), 7.66 (d, J = 16.0 Hz, H-A), 7.65 (d, J = 16.0 Hz, H-A), 7.23, 7.21, 7.20, 7.17 (4xbs, H-Ph), 7.10, 7.09, 7.09 (4xd, J = 8.3 Hz, H-Ph), 6.83 (bdd, J = 8.2, 1.8 Hz, H-Ph), 6.46 (d, J = 16.1 Hz, H-B), 6.44 (d, J = 15.9 Hz, H-B), 6.42 (d, J = 16.1 Hz, H-B), 6.41 (d, J = 15.9 Hz, H-B), 5.38 (t, J = 9.4 Hz, H-3 (7bα)), 5.37 (d, J = 4.0 Hz, H-1 (7aα)), 5.20 (d, J = 3.7 Hz, H-1 (7bα)), 5.11 (t, J = 9.3 Hz, H-3 (7bβ)), 4.85 (t overlapped with HDO, H-2 (7aβ), 4.77 (d, J = 7.9 Hz, H-1 (7aβ)), 4.74 (dd, J = 10.0, 3.7 Hz, H-2 (7aα)), 4.67 (d, J = 7.8 Hz, H-1 (7bβ)), 4.60–4.46 (m, 4×H-6a), 4.44–4.34 (m, 4×H-6b), 4.19 (ddd, J = 10.3, 5.1, 2.2 Hz, H-5 (7bα)), 4.15–4.10 (m, H-5, (7aα)), 4.01 (dd, J = 10.0, 8.9 Hz, H-3 (7aα)), 3.91, 3.90 (8xs, OCH3), 3.71 (ddd, J = 7.6, 4.6, 1.7 Hz, H-5, (7bβ)), 3.68–3.63 (m, H-5, (7aβ)), 3.66 (t, J = 9.2, H-3 (7aβ), 3.65 (dd, J = 9.8, 3.7 Hz, H-2 (7bα)), 3.64 (t, J = 9.6 Hz, H-4 (7bβ)), 3.63 (t, J = 9.7 Hz, H-4 (7bα)), 3.53 (t, J = 9.6 Hz, H-4 (7aα)), 3.52 (t, J = 9.5 Hz, H-4 (7aβ)), 3.41 (dd, J = 9.6, 7.8 Hz, H-2 (7bβ)). 13C NMR (101 MHz, CD3OD) δ 169.3, 2×169.1, 3×169.0, 168.8, 168.5 (8×COO), 98.3 (C-1 (7bβ)), 96.6 (C-1 (7aβ)), 94.0 (C-1 (7bα)), 91.4 (C-1 (7aα)).
- 2,6,1′-Tri-O-feruloyl sucrose (6a) and 6,1′,4′-tri-O-feruloyl sucrose (6b) (1.9:1), Rf = 0.47 (CHCl3:MeOH—3:1). 1H NMR (400 MHz, CD3OD) δ 7.70–7.59 (m, 5×H-A), 7.50 (d, J = 15.9 Hz, H-A (6a)), 7.31–6.98 (m, 12H-Ph), 6.81 (d, J = 8.2 Hz, H-Ph (6a)), 6.81 (d, J = 8.2 Hz, H-Ph (6b)), 6.80 (d, J = 8.2 Hz, H-Ph (6b)), 6.79 (d, J = 8.2 Hz, H-Ph (6a)), 6.77 (d, J = 8.2 Hz, H-Ph (6a)), 6.75 (d, J = 8.2 Hz, H-Ph (6b)), 6.54 (d, J = 16.0 Hz, H-B (6b)), 6.41 (d, J = 15.9 Hz, H-B (6b)), 6.38 (d, J = 15.9 Hz, H-B (6b)), 6.47 (d, J = 15.9 Hz, (6a)), 6.40 (d, J = 15.9 Hz, (6a)), 6.32 (d, J = 15.9 Hz, H-B (6a)), 5.74 (d, J = 3.7 Hz, H-1 (6a)), 5.53 (d, J = 3.8 Hz, H-1 (6b)), 5.41 (t, J = 7.5 Hz, H-4′ (6b)), 4.84 (dd, H-2 (6a) overlapped with HDO), 4.61 (bd, J = 10.0 Hz, H-6a (6b)), 4.56 (dd, J = 11.5, 1.7 Hz, H-6a (6a)), 4.51 (d, J = 12.2 Hz, H-1′a (6b)), 4.49 (d, J = 7.9 Hz, H-3′ (6b)), 4.35 (d, J = 12.2 Hz, H-1′b (6b)), 4.32 (dd, J = 11.7, 6.5 Hz, H-6b (6a)), 4.26 (d, J = 11.9 Hz, H-1′a (6a)), 4.29–4.21 (m, H-5 (6a), H-5 (6b) and H-6b (6b)), 4.17 (d, J = 11.9 Hz, H-1′b (6a)), 4.14 (d, J = 8.5 Hz, H-3′ (6a)), 4.10 (t, J = 8.2 Hz, H-4′ (6a)), 4.09–3.98 (m, H-5′ (6b)), 4.05 (t, J = 9.6 Hz, H-3 (6a)), 4.01–3.76 (m, H-6′a (6b), H-6′a (6a), H-6′b (6b), H-5′ (6a) and H-6′b (6a)), 3.89, 3.89, 3.88, 3.88, 3.85, 3.83 (6xs, OCH3), 3.77 (t, J = 9.3 Hz, H-3 (6b)), 3.76 (dd, H-6′ (6a)), 3.50 (dd, J = 9.8, 3.8 Hz, H-2 (6b)), 3.48 (t, J = 9.5 Hz, H-4 (6a)), 3.32 (t, H-4 (6b) overlapped with CD3OD). 13C NMR (101 MHz, CD3OD) δ 169.4, 169.2, 168.9, 168.5, 2×168.4 (6×COO), 104.7 (C-2′ (6b)), 103.9 (C-2′ (6a)), 94.0 (CH-1 (6b)), 91.1 (CH-1 (6a)).
- 6,1′-Di-O-feruloyl sucrose (6c). White amorphous solid; = +11.1° (c = 1.0, CH3OH), Rf = 0.50 (CHCl3:MeOH—3:1). 1H NMR (400 MHz, CD3OD) δ 7.63 (2×d, J = 15.9 Hz, 2H, 2×H-A), 7.21 (d, J = 1.9 Hz, 1H, H-Ar), 7.18 (d, J = 2.0 Hz, 1H, H-Ar), 7.08 (dd, J = 8.2, 1.9 Hz, 1H, H-Ar), 7.07 (dd, J = 8.2, 1.9 Hz, 1H, H-Ar), 6.81 (d, J = 8.2 Hz, 1H, H-Ar), 6.80 (d, J = 8.1 Hz, 1H, H-Ar), 6.43 (d, J = 15.9 Hz, 1H, H-B), 6.37 (d, J = 15.9 Hz, 1H, H-B), 5.47 (d, J = 3.8 Hz, 1H, H-1), 4.53 (dd, J = 11.9, 2.0 Hz, 1H, H-6a), 4.44 (d, J = 12.1 Hz, 1H, H-1′a), 4.29 (d, J = 12.1 Hz, 1H, H-1′b), 4.27 (dd, J = 11.9, 6.4 Hz, 1H, H-6b), 4.19–4.13 (m, 1H, H-5), 4.18 (d, J = 8.5 Hz, 1H, H-3′), 4.11 (t, J = 8.1 Hz, 1H, H-4′), 3.89 (s, 3H, OCH3), 3.88 (s, 3H, OCH3), 3.87–3.77 (m, 3H, H-6′a, H-5′, H-6′b), 3.74 (dd, J = 9.8, 8.9 Hz, 1H, H-3), 3.48 (dd, J = 9.8, 3.9 Hz, 1H, H-2), 3.34 (t, J = 9.6 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.2 (COO), 168.5 (COO), 150.7 (C-Ar), 150.6 (C-Ar), 149.4 (C-Ar), 149.3 (C-Ar), 147.4 (CH-A), 147.1 (CH-A), 127.7 (C-Ar), 127.6 (C-Ar), 124.3 (CH-Ar), 124.3 (CH-Ar), 116.5 (CH-Ar), 116.4 (CH-Ar), 115.3 (CH-B), 115.0 (CH-B), 111.7 (2×CH-Ar), 104.3 (C-2′), 93.9 (C-1), 84.0 (C-5′), 78.8 (C-3′), 75.6 (C-4′), 74.6 (C-3), 73.0 (C-2), 72.1 (C-5), 72.0 (C-4), 65.1 (C-6), 64.1 (C-1′), 64.0 (C-6′), 56.5 (2×OCH3). HRMS (ESI): m/z calcd. for C32H38O17Na ([M + Na]+) 717.20012, found 717.20015.
- 1-Feruloyl-β-d-fructopyranose (8d), 1-feruloyl-α-d-fructofuranose (8b), 6-feruloyl-β-d-fructofuranose (8c). (1:1.2:1.4), Rf = 0.42 (CHCl3:MeOH–3:1). 13C NMR (101 MHz, CD3OD) δ 105.2 (C-2, 8b), 103.2 (C-2, 8c), 98.2 (C-2, 8d).
- 6-O-Feruloyl-α,β-d-glucopyranose. (7c, α:β—1:1), Rf = 0.39 (CHCl3:MeOH—3:1). 1H NMR (400 MHz, CD3OD) δ 7.63 (2×d, J = 15.9 Hz, 2H, 2×H-A), 7.18 (2×d, J = 1.9 Hz, 2H, 2×H-Ph), 7.07 (2×dd, J = 8.2, 2.0 Hz, 2H, 2×H-Ph), 6.82 (2×d, J = 8.1 Hz, 2H, 2×H), 6.36 (2×d, J = 15.9 Hz, 2H, 2×H-B), 5.11 (d, J = 3.7 Hz, 1H, H-1α), 4.51 (d, J = 7.9 Hz, 1H, H-1β), 4.51 (dd, J = 11.9, 2.2 Hz, 1H, H-6a), 4.46 (dd, J = 11.9, 2.3 Hz, 1H, H-6a), 4.34 (dd, J = 11.9, 5.5 Hz, 2H, H-6b), 4.31 (dd, J = 12.0, 5.8 Hz, 1H, H-6b), 4.04 (ddd, J = 10.1, 5.4, 2.3 Hz, 1H, H-5), 3.89 (2×s, 6H, 2×OCH3), 3.70 (t, J = 9.2 Hz, 1H, H-3α), 3.55 (ddd, J = 9.7, 5.8, 2.1 Hz, 1H, H-5), 3.42–3.33 (m, 4H, 2×H-4, H-2α, H-3β), 3.17 (dd, J = 9.2, 7.9 Hz, 1H, H-2β). 13C NMR (101 MHz, CD3OD) δ 169.2 (COO), 169.1 (COO), 150.8 (C-Ph), 150.7 (C-Ph), 149.5 (2×C-Ph), 147.0 (CH-A), 146.9 (CH-A), 127.8 (2×C-Ph), 124.1 (2×CH-Ph), 116.6 (2×CH-Ph), 115.4 (2×CH-B), 111.9 (2×CH-Ph), 98.3 (C-1β), 94.1 (C-1α), 76.3 (C-2β), 75.6 (C-5), 74.9 (C-3α), 78.0, 73.9, 72.1, 71.8 (C-2α, C-3β, 2×C-4), 70.9 (C-5), 65.0, 64.9 (2×C-6), 56.6 (2×OCH3).
- 6-O-Feruloyl sucrose (6d), Rf = 0.25 (CHCl3:MeOH—3:1). 1H NMR (400 MHz, CD3OD) δ 7.65 (d, J = 15.9 Hz, 1H, H-A), 7.19 (d, J = 2.0 Hz, 1H, H-Ar), 7.08 (dd, J = 8.3, 2.0 Hz, 1H, H-Ar), 6.80 (d, J = 8.1 Hz, 1H, H-Ar), 6.37 (d, J = 15.9 Hz, 1H, H-B), 5.40 (d, J = 3.8 Hz, 1H, H-1), 4.50 (dd, J = 11.7, 7.4 Hz, 1H, H-6a), 4.42 (dd, J = 11., 3.3 Hz, 1H, H-6b), 4.13 (d, J = 8.2 Hz, 1H, H-3′), 4.08 (t, J = 7.9 Hz, 1H, H-4′), 3.99 (td, J = 11.5, 3.2 Hz, 1H, H-5), 3.90 (s, 3H, OCH3), 3.89–3.81 (m, 2H, H-6′a, H-5′), 3.77–3.69 (m, 2H, H-6′b, H-3), 3.67 (d, J = 12.3 Hz, 1H, H-1′a), 3.63 (d, J = 12.5 Hz, 1H, H-1′b), 3.48 (dd, J = 9.8, 3.8 Hz, 1H, H-2), 3.34 (t, J = 9.5 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 105.6 (C-2′), 93.5 (CH-1).
3.3. General Procedure for the Enzymatic Hydroxycinnamoylation of 2,1′:4,6-Di-O-isopropylidene Sucrose 2
- 6′-O-Coumaroyl-2,1′:4,6-di-O-isopropylidene sucrose (9a). White amorphous solid; = +55.9° (c = 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.64 (d, J = 15.9 Hz, 1H, H-A), 7.46 (d, J = 8.7 Hz, 2H, H-Ph), 6.81 (d, J = 8.6 Hz, 2H, H-Ph), 6.35 (d, J = 15.9 Hz, 1H, H-B), 6.05 (d, J = 3.7 Hz, 1H, H-1), 4.47–4.41 (m, 1H, H-6′a), 4.31–4.22 (m, 1H, H-6′b), 4.13 (d, J = 12.3 Hz, 1H, H-1′a), 4.08–4.03 (m, 2H, H-4′, H-5′), 3.92–3.82 (m, 3H, H-3, H-5, H-6a), 3.75–3.67 (m, 3H, H-2, H-6b, H-3′), 3.55 (t, J = 9.4 Hz, 1H, H-4), 3.44 (d, J = 12.3 Hz, 1H, H-1′b), 1.50 (s, 3H, CH3), 1.47 (s, 3H, CH3), 1.38 (s, 6H, 2×CH3). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 161.2 (C-Ph),146.7 (CH-A), 131.2 (CH-Ph), 127.2 (C-Ph), 116.8 (CH-Ph), 115.0 (CH-B), 105.2 (C-2′), 102.8 (C-izopr), 100.8 (C-izopr), 92.4 (C-1), 81.1 (C-5′), 80.0 (C-3′), 77.9 (C-4′), 75.2 (C-2), 74.8 (C-4), 70.9 (C-3), 67.5 (C-6′), 66.9 (C-1′), 64.6 (C-5), 63.4 (C-6), 29.5 (CH3), 25.5 (CH3), 24.4 (CH3), 19.3 (CH3). HRMS (ESI): m/z calcd. for C27H36O13Na ([M + Na]+) 591.20481, found 591.20485.
- 6′-O-Feruloyl-2,1′:4,6-di-O-isopropylidene sucrose (9b). White amorphous solid; = +57.7° (c = 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.63 (d, J = 15.9 Hz, 1H, H-A), 7.07 (dd, J = 8.2, 2.0 Hz, 1H, H-Ph), 6.81 (d, J = 8.2 Hz, 2H, H-Ph), 6.38 (d, J = 15.9 Hz, 1H, H-B), 6.05 (d, J = 3.8 Hz, 1H, H-1), 4.48–4.42 (m, 1H, H-6′a), 4.30–4.22 (m, 1H, H-6′b), 4.13 (d, J = 12.3 Hz, 1H, H-1′a), 4.08–4.03 (m, 2H, H-4′, H-5′), 3.89 (s, 3H, OCH3), 3.89–3.83 (m, 3H, H-3, H-5, H-6a), 3.75–3.66 (m, 3H, H-2, H-6b, H-3′), 3.55 (t, J = 9.3 Hz, 1H, H-4), 3.44 (d, J = 12.3 Hz, 1H, H-1′b), 1.50 (s, 3H, CH3), 1.47 (s, 3H, CH3), 1.38 (s, 6H, 2×CH3). 13C NMR (101 MHz, CD3OD) δ 168.9 (COO), 150.6 (C-Ph), 149.3 (C-Ph), 147.0 (CH-A), 127.7 (C-Ph), 124.1 (CH-Ph), 116.5 (CH-Ph), 115.3 (CH-B), 111.7 (CH-Ph), 105.2 (C-2′), 102.8 (C-izopr), 100.8 (C-izopr), 92.4 (C-1), 81.1 (C-5′), 80.0 (C-3′), 77.9 (C-4′), 75.2 (C-2), 74.8 (C-4), 70.9 (C-3), 67.5 (C-6′), 66.9 (C-1′), 64.6 (C-5), 63.4 (C-6), 56.5 (OCH3), 29.5 (CH3), 25.5 (CH3), 24.4 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C28H38O14Na ([M + Na]+) 621.21538; found 621.21587.
3.4. General Procedure for the Enzymatic Hydroxycinnamoylation of 4,6-O-isopropylidene Sucrose 3
- 1′-O-Coumaroyl-4,6-O-isopropylidene sucrose (10a). White amorphous solid, = +15.2° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.65 (d, J = 15.9 Hz, 1H, H-A), 7.47 (d, J = 8.7 Hz, 2H, H-Ph), 6.81 (d, J = 8.7 Hz, 2H, H-Ph), 6.36 (d, J = 15.9 Hz, 1H, H-B), 5.43 (d, J = 4.0 Hz, 1H, H-1), 4.42 (d, J = 12.1 Hz, 1H, H-1′a), 4.23 (d, J = 12.1 Hz, 1H, H-1′b), 4.16 (d, J = 8.6 Hz, 1H, H-3′), 4.09 (t, J = 8.4 Hz, 1H, H-4′), 3.87 (t, J = 9.7 Hz, 1H), 3.94–3.83 (m, 2H, H-5, H-6a), 3.82–3.66 (m, 5H, H-5′, H-3, H-6′a, H-6′b, H-6b) 3.51 (dd, J = 9.5, 3.8 Hz, 1H, H-2), 3.51 (t, J = 9.5 Hz, 1H, H-4), 1.50 (s, 3H, CH3), 1.38 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 168.4 (COO), 161.4 (C-Ph), 147.1 (CH-A), 131.3 (CH-Ph), 127.1 (C-Ph), 116.8 (CH-Ph), 114.7 (CH-B), 104.2 (C-2′), 100.8 (C-Izopr), 94.7 (C-1), 83.9 (C-5′), 78.5 (C-3′), 75.1 (C-4), 74.7 (C-4′), 73.7 (C-2), 71.9 (C-3), 65.4 (C-5), 63.7 (C-1′), 63.2, 62.9 (C-6, C-6′), 29.4 (CH3), 19.3 (CH3). HRMS (ESI): m/z calcd. for C24H32O13Na ([M + Na]+) 551.17351; found 551.17349.
- 4′-O-Coumaroyl-4,6-O-isopropylidene sucrose (11a). White foam, = +9.8° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.68 (d, J = 15.9 Hz, 1H, H-A), 7.48 (d, J = 8.7 Hz, 2H, H-Ph), 6.82 (d, J = 8.7 Hz, 2H, H-Ph), 6.38 (d, J = 15.9 Hz, 1H, H-B), 5.43 (d, J = 4.0 Hz, 1H, H-1), 5.38 (t, J = 7.6 Hz, 1H, H-4′), 4.47 (d, J = 7.9 Hz, 1H, H-3′), 4.02–3.96 (m, 2H, H-5′, H-5), 3.93 (dd, J = 10.2, 5.2 Hz, 1H, H-6a), 3.81 (t, J = 9.3 Hz, 1H, H-3), 3.77–3.71 (m, 3H, H-6′a, H-6′b, H-6b), 3.68 (d, J = 12.4 Hz, 1H, H-1′a), 3.61 (d, J = 12.4 Hz, 1H, H-1′b), 3.53 (dd, J = 9.4, 4.1 Hz, 1H, H-2), 3.52 (t, J = 9.4 Hz, 1H, H-4), 1.51 (s, 3H, CH3) 1.40 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 168.6 (COO), 161.5 (C-Ph), 147.5 (CH-A), 131.3 (CH-Ph), 127.0 (C-Ph), 116.9 (CH-Ph), 114.5 (CH-B), 105.9 (C-2′), 100.8 (C-Izopr), 94.3 (C-1), 82.5 (C-5′), 77.8 (C-4′), 77.0 (C-3′), 75.1 (C-4), 73.7 (C-2), 72.0 (C-3), 65.4 (C-5), 63.6 (C-1′), 63.5 (C-6′), 63.2 (C-6), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C24H32O13Na ([M + Na]+) 551.17351; found 551.17356.
- 6′-O-Coumaroyl-4,6-O-isopropylidene sucrose (12a). White amorphous solid, = +52.3° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.64 (d, J = 16.0 Hz, 1H, H-A), 7.46 (d, J = 8.7 Hz, 2H, H-Ph), 6.81 (d, J = 8.6 Hz, 2H, H-Ph), 6.35 (d, J = 16.0 Hz, 1H, H-B), 5.37 (d, J = 4.0 Hz, 1H, H-1), 4.44–4.32 (m, 2H, H-6′a, H-6′b), 4.14 (d, J = 7.9 Hz, 1H, H-3′), 4.05 (t, J = 7.9 Hz, 1H, H-4′), 4.00 (ddd, J = 7.9, 6.0, 4.3 Hz, 1H, H-5′), 3.96–3.89 (m, 2H, H-5, H-6a), 3.78 (t, J = 9.3 Hz, 1H, H-3), 3.75–3.69 (m, 1H, H-6b), 3.65 (d, J = 12.2 Hz, 1H, H-1′a), 3.62 (d, J = 12.1 Hz, 1H, H-1′b), 3.49 (t, J = 9.4 Hz, 1H, H-4), 3.48 (dd, J = 9.4, 4.0 Hz, 1H, H-2), 1.49 (s, 3H, CH3), 1.37 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 161.3 (C-Ph), 146.8 (CH-A), 131.2 (CH-Ph), 127.2 (C-Ph), 116.8 (CH-Ph), 115.0 (CH-B), 105.7 (C-2′), 100.8 (C-Izopr), 94.1 (C-1), 80.8 (C-5′), 78.6 (C-2′), 76.8 (C-4′), 75.3 (C-4), 74.1 (C-2), 72.1 (C-3), 66.5 (C-6′), 65.3 (C-5), 63.5, 63.4 (C-1′, C-6), 29.5 (CH3), 19.3 (CH3). HRMS (ESI): m/z calcd. for C24H32O13Na ([M + Na]+) 551.17351; found 551.17339.
- 1′,4′-Di-O-coumaroyl-4,6-O-isopropylidene sucrose (13a). White foam, = +30.4° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.69 (d, J = 15.9 Hz, 1H, H-A1), 7.68 (d, J = 15.9 Hz, 1H, H-A2), 7.49 (d, J = 8.5 Hz, 2H, H-Ph1), 7.47 (d, J = 8.5 Hz, 2H, H-Ph2), 6.81 (d, J = 8.6 Hz, 2H, H-Ph1), 6.81 (d, J = 8.6 Hz, 2H, H-Ph2), 6.39 (d, J = 15.8 Hz, 1H, H-B1), 6.38 (d, J = 15.9 Hz, 1H, H-B2), 5.50 (d, J = 4.0 Hz, 1H, H-1), 5.41 (t, J = 7.8 Hz, 1H, H-4′), 4.48 (d, J = 8.0 Hz, 1H, H-3′), 4.47 (d, J = 12.2 Hz, 1H, H-1′a), 4.32 (d, J = 12.2 Hz, 1H, H-1′b), 4.05–3.98 (m, 2H, H-5, H-5′), 3.94 (dd, J = 10.3, 5.2 Hz, 1H, H-6a), 3.80 (t, J = 9.4 Hz, 1H, H-3), 3.81–3.72 (m, 3H, H-6′a, H-6′b, H-6b), 3.55 (dd, J = 9.5, 4.1 Hz, 1H, H-2), 3.54 (t, J = 9.4 Hz, 1H, H-4), 1.52 (s, 3H, CH3), 1.40 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 168.5 (COO), 168.4 (COO), 161.5 (C-Ph), 161.4 (C-Ph), 147.6 (CH-A), 147.3 (CH-A), 131.4 (2×CH-Ph), 131.3 (2×CH-Ph), 127.1 (C-Ph), 127.0 (C-Ph), 116.9 (4×CH-Ph), 114.6 (CH-B), 114.4 (CH-B), 104.8 (C-2′), 100.8 (C-Izopr), 94.9 (C-1), 82.6 (C-5′), 77.2 (C-4′), 77.0 (C-3′), 75.2 (C-4), 73.8 (C-2), 72.1 (C-3), 65.5 (C-5), 63.7, 63.6 (C-1′, C-6′), 63.2 (C-6), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C33H38O15Na ([M + Na]+) 697.21029; found 697.21004.
- 1′,6′-Di-O-coumaroyl-4,6-O-isopropylidene sucrose (14a). White amorphous solid, = −14.5° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.67 (d, J = 15.9 Hz, 1H, H-A1), 7.64 (d, J = 16.0 Hz, 1H, H-A2), 7.48 (d, J = 8.5 Hz, 2H, H-Ph1), 7.46 (d, J = 8.6 Hz, 2H, H-Ph2), 6.81 (d, J = 8.8 Hz, 2H, H-Ph1), 6.80 (d, J = 8.8 Hz, 2H, H-Ph2), 6.38 (d, J = 15.9 Hz, 1H, H-B1), 6.38 (d, J = 16.0 Hz, 1H, H-B2), 5.43 (d, J = 4.0 Hz, 1H, H-1), 4.46–4.36 (m, 3H, H-1′a, H-6′a, H-6′b), 4.31 (d, J = 12.1 Hz, 1H, H-1′b), 4.17 (d, J = 8.2 Hz, 1H, H-3′), 4.09 (t, J = 8.2 Hz, 1H, H-4′), 4.01 (ddd, J = 8.1, 5.8, 4.2 Hz, 1H, H-5′), 3.98–3.93 (m, 1H, H-5), 3.91 (dd, J = 10.3, 5.2 Hz, 1H, H-6a), 3.78 (t, 9.2, 1H, H-3), 3.73 (t, J = 10.2 Hz, 1H, H-6b), 3.51 (t, J = 9.4 Hz, 1H, H-4), 3.50 (dd, J = 9.4, 4.2 Hz, 1H, H-2), 1.49 (s, 3H, CH3), 1.37 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 168.4 (COO), 161.4 (C-Ph1), 161.3 (C-Ph2), 147.2 (CH-A1), 146.8 (CH-A2), 131.3 (CH-Ph1), 131.3 (CH-Ph2), 127.2 (C-Ph1), 127.1 (C-Ph2), 116.8 (CH-Ph1), 116.8 (CH-Ph2), 115.0 (CH-B1), 114.7 (CH-B2), 104.6 (C-2′), 100.8 (C-Izopr), 94.6 (C-1), 80.9 (C-5′), 78.6 (C-3′), 76.1 (C-4′), 75.3 (C-4), 74.0 (C-2), 72.1 (C-3), 66.1 (C-6′), 65.4 (C-5), 63.8 (C-1′), 63.3 (C-6), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C33H38O15Na ([M + Na]+) 697.21029; found 697.21069.
- 1′-O-Feruloyl-4,6-O-isopropylidene sucrose (10b). White amorphous solid, = +14.7° (c 1.0, MeOH). 1H NMR (400 MHz, CD3OD) δ 7.65 (d, J = 15.9 Hz, 1H, H-A), 7.19 (d, J = 1.9 Hz, 1H, H-Ph), 7.08 (dd, J = 8.1, 1.9 Hz, 1H, H-Ph), 6.81 (d, J = 8.2 Hz, 1H, H-Ph), 6.39 (d, J = 15.9 Hz, 1H, H-B), 5.43 (d, J = 4.0 Hz, 1H, H-1), 4.42 (d, J = 12.2 Hz, 1H, H-1′a), 4.24 (d, J = 12.1 Hz, 1H, H-1′b), 4.17 (d, J = 8,6 Hz, 1H, H-3′), 4.09 (t, J = 8.5 Hz, 1H, H-4′), 3,93–3,83 (m, 2H, H-5, H-6a), 3.89 (s, 3H, OCH3), 3.82–3.67 (m, 4H, H-5′, H-6′a, H-6′b, H-6b), 3.78 (t, J = 9.8 Hz, 1H, H-3), 3.52 (dd, J = 9.6, 4.0 Hz, 1H, H-2), 3.51 (t, J = 9.3 Hz, 1H, H-4), 1.50 (s, 3H, CH3), 1.38 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 168.4 (COO), 150.7 (C-Ph), 149.4 (C-Ph), 147.4 (C-A), 127.6 (C-Ph), 124.3 (CH-Ph), 116.5 (CH-Ph), 114.9 (CH-B), 111.7 (CH-Ph), 104.2 (C-2′), 100.8 (C-Izopr), 94.7 (C-1), 83.9 (C-5′), 78.5 (C-3′), 75.1 (C-4), 74.7 (C-4′), 73.7 (C-2), 71.9 (C-3), 65.4 (C-5), 63.7 (C-1′), 63.2 (C-6), 62.9 (C-6′), 56.5 (OCH3), 29.4 (CH3), 19.3 (CH3). HRMS (ESI): m/z calcd. for C25H34O14 [M + Na]+ = 581.18408, found 581.18411.
- 4′-O-Feruloyl-4,6-O-isopropylidene sucrose (11b). White foam, = +8.2° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.69 (d, J = 15.9 Hz, 1H, H-A), 7.22 (d, J = 2.0 Hz, 1H, H-Ph), 7.10 (dd, J = 8.2, 2.0 Hz, 1H, H-Ph), 6.82 (d, J = 8.1 Hz, 1H, H-Ph), 6.42 (d, J = 15.8 Hz, 1H, H-B), 5.43 (d, J = 4.0 Hz, 1H, H-1), 5.38 (t, J = 7.6 Hz, 1H, H-4′), 4.47 (d, J = 7.9 Hz, 1H, H-3′), 4.03–3.96 (m, 2H, H-5′, H-5), 3.94 (dd, J = 10.6, 5.2 Hz, 1H, H-6a), 3.90 (s, 3H, OCH3), 3.81 (t, J = 9.3 Hz, 1H, H-3), 3.77–3.70 (m, 3H, H-6′a, H-6′b, H-6), 3.68 (d, J = 12.4 Hz, 1H, H-1′a), 3.61 (d, J = 12.3 Hz, 1H, H-1′b), 3.53 (dd, J = 9.4, 4.1 Hz, 1H, H-2), 3.52 (t, J = 9.4 Hz, 1H, H-4), 1.52 (s, 3H), 1.40 (s, 3H). 13C NMR (101 MHz, CD3OD) δ 168.6 (COO), 150.9 (C-Ph), 149.4 (C-Ph), 147.7 (CH-A), 127.6 (C-Ph), 124.3 (CH-Ph), 116.5 (CH-Ph), 114.8 (CH-B), 111.8 (CH-Ph), 105.9 (C-2′), 100.8 (C-Izopr), 94.3 (C-1), 82.5 (C-5′), 77.8 (C-4′), 77.0 (C-3′), 75.2 (C-4), 73.9 (C-2), 72.0 (C-3), 65.5 (C-5), 63.6, 63.5 (C-6′, C-1′), 63.3 (C-6), 56.5 (OCH3), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C25H34O14 [M + Na]+ = 581.18408; found 581.18409.
- 6′-O-Feruloyl-4,6-O-isopropylidene sucrose (12b). White foam, = +49.0° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.63 (d, J = 15.9 Hz, 1H, H-A), 7.20 (d, J = 2.0 Hz, 1H, H-Ph), 7.07 (dd, J = 8.2, 1.9 Hz, 1H, H-Ph), 6.81 (d, J = 8.2 Hz, 1H, H-Ph), 6.40 (d, J = 15.9 Hz, 1H, H-B), 5.36 (d, J = 4.0 Hz, 1H, H-1), 4.39 (dd, J = 11.8, 5.9 Hz, 1H, H-6′a), 4.39 (dd, J = 11.5, 4.3 Hz, 1H, H-6′b), 4.15 (d, J = 7.9 Hz, 1H, H-3′), 4.05 (t, J = 7.9 Hz, 1H, H-4′), 4.00 (ddd, J = 7.7, 5.6, 4.2 Hz, 1H, H-5′), 3.96 (bdd, J = 10.0, 4.9 Hz, 1H, H-5), 3.91 (dd, J = 10.4, 4.4 Hz, 1H, H-6a), 3.90 (s, 3H, OCH3), 3.79 (t, J = 9.3 Hz, 1H, H-3), 3.72 (t, J = 10.1 Hz, 1H, H-6b), 3.67 (d, J = 12.4 Hz, 1H, H-1′a), 3.63 (d, J = 12.3 Hz, 1H, H-1′b), 3.49 (t, J = 9.0 Hz, 1H, H-4), 3.49 (dd, J = 9.2, 4.5 Hz, 1H, H-2), 1.49 (s, 3H, CH3), 1.37 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 150.6 (C-Ph), 149.4 (C-Ph), 147.1 (C-A), 127.7 (C-Ph), 124.2 (CH-Ph), 116.5 (CH-Ph), 115.3 (CH-B), 111.7 (CH-Ph), 105.7 (C-2′), 100.8 (C-Izopr), 94.2 (C-1), 80.8 (C-5′), 78.6 (C-3′), 76.8 (C-4′), 75.3 (C-4), 74.1 (C-2), 72.1 (C-3), 66.4 (C-6′), 65.3 (C-5), 2×63.4 (C-1′, C-6), 56.5 (OCH3), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C25H34O14 [M + Na]+ = 581.18408; found 581.18412.
- 1′,4′-Di-O-feruloyl-4,6-O-isopropylidene sucrose (13b). Colorless foam, = +39.7° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.69 (d, J = 16.0 Hz, 1H, H-A1), 7.67 (d, J = 16.0 Hz, 1H, H-A2), 7.21 (d, J = 2.2 Hz, 1H, H-Ph1), 7.19 (d, J = 1.8 Hz, 1H, H-Ph1), 7.09 (dd, J = 8.2, 2.1 Hz, 1H, H-Ph1), 7.08 (dd, J = 8.3, 1.9 Hz, 1H, H-Ph2), 6.81 (d, J = 8.1 Hz, 2H, H-Ph1, H-Ph2), 6.43 (d, J = 16.0 Hz, 1H, H-B1), 6.41 (d, J = 15.9 Hz, 1H, H-B2), 5.50 (d, J = 4.0 Hz, 1H, H-1), 5.41 (t, J = 7.6 Hz, 1H, H-4′), 4.49 (d, J = 8.0 Hz, 1H, H-3′), 4.47 (d, J = 12.3 Hz, 1H, H-1′a), 4.33 (d, J = 12.2 Hz, 1H, H-1′b), 4.05 (ddd, J = 10.2, 5.2, 3.5 Hz, 1H, H-5′), 4.05–3.99 (m, 1H, H-5), 3.95 (dd, J = 10.3, 5.2 Hz, 1H, H-6a), 3.89 (s, 3H, OCH3), 3.88 (s, 3H, OCH3), 3.80 (t, J = 9.2 Hz, 1H, H-3), 3.79–3.71 (m, 3H, H-6′a, H-6′b, H-6b), 3.55 (dd, J = 9.5, 4.1 Hz, 1H, H-2), 3.54 (t, J = 9.6 Hz, 1H, H-4), 1.52 (s, 3H, CH3), 1.40 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 168.5 (COO), 168.4 (COO), 150.9 (C-Ph1), 150.8 (C-Ph2), 2×149.4 (C-Ph1,C-Ph2), 147.8 (CH-A1), 147.6 (CH-A2), 2×127.6 (C-Ph1, C-Ph2), 124.4 (CH-Ph1), 124.3 (CH-Ph2), 2×116.5 (CH-Ph1, CH-Ph2), 114.9 (CH-B1), 114.7 (CH-B2), 2×111.7 (CH-Ph1, CH-Ph2), 104.8 (C-2′), 100.8 (C-Izopr), 94.9 (C-1), 82.6 (C-5′), 77.3 (C-4′), 77.0 (C-3′), 75.2 (C-4), 73.8 (C-2), 72.1 (C-3), 65.5 (C-5), 63.7 (C-1′), 63.7 (C-6′), 63.3 (C-6), 2×56.5 (2×OCH3), 29.5 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C35H42O17 [M + Na]+ = 757.23142; found 757.23129.
- 1′,6′-Di-O-feruloyl-4,6-O-isopropylidene sucrose (14b). White amorphous solid, = −14.0° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.65 (d, J = 15.9 Hz, 1H, H-A1), 7.62 (d, J = 15.9 Hz, 1H, H-A2), 7.19 (d, J = 2.0 Hz, 1H, H-Ph1), 7.18 (d, J = 2.0 Hz, 1H, H-Ph2), 7.07 (dd, J = 8.3, 2.0 Hz, 1H, H-Ph1), 7.05 (dd, J = 8.4, 2.0 Hz, 1H, H-Ph2), 6.81 (d, J = 8.2 Hz, 1H, H-Ph1), 6.80 (d, J = 8.2 Hz, 1H, H-Ph1), 6.42 (d, J = 15.9 Hz, 1H, H-B1), 6.40 (d, J = 15.9 Hz, 1H, H-B2), 5.42 (d, J = 4.0 Hz, 1H, H-1), 4.44 (d, J = 12.2 Hz, 1H, H-1′a), 4.42–4.41 (m, 2H, H-6′a, H-6′b), 4.32 (d, J = 12.1 Hz, 1H, H-1′b), 4.19 (d, J = 8.2 Hz, 1H, H-3′), 4.09 (t, J = 8.2 Hz, 1H, H-4′), 4.03 (ddd, J = 10.1, 6.9, 4.6 Hz, 1H, H-5′), 3.99 (td, J = 10.2, 5.1 Hz, 1H, H-5), 3.91 (dd, J = 10.4, 5.2 Hz, 1H, H-6a), 3.88 (s, 6H, OCH3), 3.79 (t, J = 9.4 Hz, 1H, H-3), 3.73 (t, J = 10.5 Hz, 1H, H-6b), 3.51 (t, J = 9.5 Hz, 1H, H-4), 3.50 (dd, J = 9.5, 4.0 Hz, 1H, H-2), 1.49 (s, 3H, CH3), 1.36 (s, 3H, CH3). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 168.4 (COO), 150.7 (C-Ph1), 150.6 (C-Ph2), 2×149.3 (C-Ph1,2), 147.5 (CH-A1), 147.1 (CH-A2), 127.7 (C-Ph1), 127.6 (C-Ph2), 2×124.3 (2×CH-Ph1,2), 116.5 (CH-Ph1), 116.4 (CH-Ph2), 115.3 (CH-B1), 114.9 (CH-B2), 2×111.7 (2×CH-Ph1,2), 104.6 (C-2′), 100.8 (C-Izopr), 94.8 (C-1), 80.9 (C-5′), 78.6 (C-3′), 76.1 (C-4′), 75.3 (C-4), 74.0 (C-2), 72.1 (C-3), 66.1 (C-6′), 65.4 (C-5), 63.7 (C-1′), 63.3 (C-6), 2×56.5 (2×OCH3), 29.4 (CH3), 19.4 (CH3). HRMS (ESI): m/z calcd. for C35H42O17 [M + Na]+ = 757.23142; found 757.23112
3.5. Preparation of 3′-O-acylated Sucrose 4a and 4b
- 3′-O-Coumaroyl sucrose (4a). White amorphous solid, = −8.8° (c 1.0, CH3OH), = −11.0° (c 1.03, CH3OH) [56]. 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.9 Hz, 1H, H-A), 7.51 (d, J = 8.7 Hz, 2H, H-Ph), 6.81 (d, J = 8.7 Hz, 2H, H-Ph), 6.40 (d, J = 15.9 Hz, 1H, H-B), 5.46 (d, J = 7.9 Hz, 1H, H-3′), 5.43 (d, J = 3.7 Hz, 1H, H-1), 4.37 (t, J = 7.9 Hz, 1H, H-4′), 3.96–3.88 (m, 2H, H-5′, H-5), 3.85 (dd, J = 11.8, 2.3 Hz, 1H, H-6a), 3.87–3.78 (m, 2H, H-6′a, H-6′b), 3.77 (dd, J = 12.0, 4.3 Hz, 1H, H-6b), 3.66 (t, J = 9.4 Hz, 1H, H-3), 3.66 (d, J = 12.2 Hz, 1H, H-1′a), 3.59 (d, J = 12.2 Hz, 1H, H-1′b), 3.43 (dd, J = 9.8, 3.7 Hz, 1H, H-2), 3.40 (dd, J = 9.9, 8.9 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 168.4 (COO), 161.4 (C-Ph), 147.4 (CH-A), 131.4 (2×CH-Ph), 127.2 (C-Ph), 116.8 (2×CH-Ph), 114.8 (CH-B), 104.8 (C-2′), 93.3 (C-1), 84.1 (C-5′), 79.7 (C-3′), 74.9 (C-3), 74.6 (C-5), 73.8 (C-4′), 73.1 (C-2), 71.2 (C-4), 65.3 (C-1′), 62.9 (C-6′), 62.3 (C-6).
- 3′-O-(3,4,5-Trimethoxycinnamoyl) sucrose (4b). White crystals, m.p. = 80–83 C; = +16.2° (c 1.0, CH3OH), = +5.7° (c 1.39, CH3OH) [57]; 1H NMR (400 MHz, CD3OD) δ 7.72 (d, J = 15.9 Hz, 1H, H-A), 6.98 (s, 2H, H-Ph), 6.55 (d, J = 15.9 Hz, 1H, H-B), 5.48 (d, J = 7.8 Hz, 1H, H-3′), 5.44 (d, J = 3.7 Hz, 1H, H-1), 4.39 (t, J = 7.8 Hz, 1H, H-4), 3.96–3.91 (m, 2H, H-5′, H-5), 3.88 (s, 6H, m-OCH3), 3.88–3.80 (m, 3H, H-6a, H-6′a, H-6′b), 3.79 (s, 3H, p-OCH3), 3.79–3.75 (m, 1H, H-6b), 3.67 (dd, J = 9.7, 8.9 Hz, 1H, H-3), 3.66 (d, J = 12.2 Hz, 1H, H-1′a), 3.58 (d, J = 12.2 Hz, 1H, H-1′b), 3.44 (dd, J = 9.7, 3.7 Hz, 1H, H-2), 3.40 (dd, J = 10.0, 8.9 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 167.7 (COO), 154.8 (2×C-Ph), 147.2 (CH-A), 141.4 (C-Ph), 131.5 (C-Ph), 117.9 (CH-B), 107.0 (2×CH-Ph), 104.8 (C-2′), 93.3 (C-1), 84.2 (C-5′), 79.8 (C-3′), 75.0 (C-3), 74.6 (C-5), 73.9 (C-4), 73.1 (C-2), 71.2 (C-4), 65.4 (C-1′), 62.9 (C-6′), 62.4 (C-6), 61.2 (p-OCH3), 56.8 (2×m-OCH3). HRMS (ESI): m/z calcd. for C24H34O15 [M + Na]+ = 585.17899; found 585.18030.
3.6. General Procedure for the Enzymatic Hydroxycinnamoylation of 3′-O-acylated Sucrose 4a and 4b
- 6,3′-Di-O-coumaroyl sucrose (15a). White amorphous solid, = −35.6° (c 1.0, CH3OH), = −72.0° (c 0.3, CH3OH) [58]. 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.9 Hz, 1H, H-A1), 7.64 (d, J = 15.9 Hz, 1H, H-A1), 7.51 (d, J = 8.7 Hz, 2H, H-Ph1), 7.47 (d, J = 8.7 Hz, 2H, H-Ph2), 6.80 (d, J = 8.7 Hz, 1H, H-Ph1), 6.79 (d, J = 8.6 Hz, 1H, H-Ph2), 6.42 (d, J = 16.1 Hz, 1H, H-B2), 6.41 (d, J = 15.9 Hz, 1H, H-B1), 5.48 (d, J = 7.9 Hz, 1H, H-3′), 5.47 (d, J = 4.1 Hz, 1H, H-1), 4.58 (dd, J = 11.9, 1.9 Hz, 1H, H-6a), 4.42 (t, J = 8.0 Hz, 1H, H-4′), 4.29 (dd, J = 11.8, 6.3 Hz, 1H, H-6b), 4.20 (ddd, J = 10.1, 6.3, 1.9 Hz, 1H, H-5), 3.97 (ddd, J = 7.9, 6.9, 2.9 Hz, 1H, H-5′), 3.91 (dd, J = 11.8, 6.9 Hz, 1H, H-6′a), 3.81 (dd, J = 11.8, 2.9 Hz, 1H, H-6′b), 3.67 (dd, J = 9.7, 8.9 Hz, 1H, H-3), 3.64 (d, J = 12.2 Hz, 1H, H-1′a), 3.59 (d, J = 12.2 Hz, 1H, H-1′b), 3.47 (dd, J = 9.7, 3.8 Hz, 1H, H-2), 3.35 (dd, J = 10.0, 8.9 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.2 (COO), 168.4 (COO), 161.4 (C-Ph1), 161.3 (C-Ph2), 147.5 (CH-A1), 146.9 (CH-A2), 131.4 (2×CH-Ph1), 131.3 (2×CH-Ph2), 127.2, 127.1 (C-Ph1, C-Ph2), 116.8 (2×CH-Ph1, 2×CH-Ph2), 115.0, 114.7 (CH-B1, CH-B2), 104.8 (C-2′), 92.9 (C-1), 84.2 (C-5′), 79.5 (C-3′), 74.9 (C-3), 74.1 (C-4′), 73.1 (C-2), 72.3 (C-5), 71.8 (C-4), 65.5 (C-1′), 65.2 (C-6), 63.8 (C-6′). HRMS (ESI): m/z calcd. for C30H34O15 [M + Na]+ = 657.17899, found 657.18914.
- 3′,6′-Di-O-coumaroyl sucrose (16a). NMR data extracted from the mixture with 15a, 1H NMR (400 MHz, CD3OD), δ 7.72 (d, J = 15.8 Hz, 1H, H-A1), 7.66 (d, J = 15.9 Hz, 1H, H-A2), 7.51 (d, J = 8.6 Hz, 1H, 2×H-Ph), 7.46 (d, J = 8.8 Hz, 2H, 2×H-Ph), 6.81 (d, J = 8.6 Hz, 4H, 4×H-Ph), 6.41 (d, J = 15.9 Hz, 1H, H-B1), 6.36 (d, J = 16.0 Hz, 1H, H-B2), 5.49 (d, J = 8.0 Hz, 1H, H-3′), 5.45 (d, J = 3.8 Hz, 1H, H-1), 4.57 (dd, J = 11.9, 7.5 Hz, 1H, H-6′a), 4.51 (dd, J = 11.9, 3.9 Hz, 1H, H-6′b), 4.45 (t, J = 7.6 Hz, 1H, H-4′), 4.19–4.12 (m, 1H, H-5′), 3.94–3.77 (m, 3H, H-5, H-6a, H-6b), 3.68 (t, J = 9.5 Hz, 1H, H-3), 3.67 (d, J = 12.2 Hz, 1H, H-1′a), 3.61 (d, J = 12.0 Hz, 1H, H-1′b), 3.44 (dd, J = 9.7, 3.8 Hz, 1H, H-2), 3.41 (t, J = 8.9 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 168.3 (COO), 161.3 (C-Ph), 161.2 (C-Ph), 147.5 (CH-A1), 146.9 (CH-A2), 131.4 (2×CH-Ph), 131.2 (2×CH-Ph), 127.5, 127.1 (C-Ph1, C-Ph2), 116.8 (2×CH-Ph1, 2×CH-Ph2), 114.8, 114.6 (CH-B1, CH-B2), 105.0 (C-2′), 93.1 (C-1), 81.2 (C-5′), 79.3 (C-3′), 74.9 (C-3), 74.1 (C-4′), 73.1 (C-2), 72.3 (C-5), 71.8 (C-4), 66.3 (C-6′), 65.1 (C-1′), 62.6 (C-6).
- 6,3′,4′-Tri-O-coumaroyl sucrose (17a). White foam, = −128.2° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.9 Hz, 1H, H-A1), 7.62 (d, J = 15.9 Hz, 1H, H-A2), 7.61 (d, J = 16.0 Hz, 1H, H-A3), 7.51 (d, J = 8.7 Hz, 2H, H-Ph1), 7.43 (d, J = 8.7 Hz, 4H, H-Ph2, H-Ph3), 6.80 (d, J = 8.6 Hz, 2H, H-Ph2), 6.79 (d, J = 8.7 Hz, 2H, H-Ph1), 6.70 (d, J = 8.7 Hz, 2H, H-Ph3), 6.48 (d, J = 16.0 Hz, 1H, H-B3), 6.40 (d, J = 15.9 Hz, 1H, H-B1), 6.31 (d, J = 16.0 Hz, 1H, H-B2), 5.81 (d, J = 7.5 Hz, 1H, H-3′), 5.68 (t, J = 7.4 Hz, 1H, H-4′), 5.52 (d, J = 3.7 Hz, 1H, H-1), 4.67–4.64 (m, 1H, H-6a), 4.34–4.22 (m, 2H, H-6b, H-5), 4.20 (ddd, J = 7.4, 4.5, 3.0 Hz, 1H, H-5′), 4.01 (dd, J = 12.2, 7.5 Hz, 1H, H-6′a), 3.85 (dd, J = 12.1, 3.8 Hz, 1H, H-6′b), 3.71 (dd, J = 9.8, 8.9 Hz, 1H, H-3), 3.67 (d, J = 12.6 Hz, 1H, H-1′a), 3.62 (d, J = 12.4 Hz, 1H, H-1′b), 3.50 (dd, J = 9.8, 3.7 Hz, 1H, H-2), 3.33 (t, signal overlapped by CD3OD, H-4). 13C NMR (101 MHz, CD3OD) δ 169.4 (COO), 168.2 (COO), 168.0 COO), 161.5 (C-Ph), 161.42 (C-Ph), 161.1 (C-Ph), 2×147.8 (CH-A1, CH-A2), 146.7 (CH-A3), 131.5 (2×CH-Ph1), 131.4, 131.3 (2×CH-Ph2, 2×CH-Ph3), 127.2 (C-Ph), 127.1 (C-Ph), 127.0 (C-Ph), 116.9, 116.8, 116.7 (2×CH-Ph1, 2×CH-Ph2, 2×CH-Ph3), 115.3 (CH-B3), 114.4 (CH-B1), 114.1 (CH-B2), 105.4 (C-2′), 93.1 (C-1), 83.0 (C-3′), 77.2 (C-3′), 76.3 (C-4′), 74.9 (C-3), 73.0 (C-2), 72.7 (C-5), 72.0 (C-4), 65.6 (C-6), 65.0 (C-1′), 64.1 (C-6′).
- 6,3′,6′-Tri-O-coumaroyl sucrose (18a). = −13.0° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.72 (d, J = 16.0 Hz, 1H, H-A1), 7.62 (d, J = 15.8 Hz, 1H, H-A2), 7.60 (d, J = 16.0 Hz, 1H, H-A3), 7.52 (d, J = 8.7 Hz, 2H, H-Ph1), 7.41 (d, J = 8.7 Hz, 2H, H-Ph2), 7.38 (d, J = 8.7 Hz, 2H, H-Ph3), 6.81 (d, J = 8.8 Hz, 2H, H-Ph1), 6.79 (d, J = 8.6 Hz, 2H, H-Ph3), 6.75 (d, J = 8.7 Hz, 2H, H-Ph2), 6.42 (d, J = 15.9 Hz, 1H, H-B1), 6.41 (d, J = 15.9 Hz, 1H, H-B2), 6.28 (d, J = 15.9 Hz, 1H, H-B3), 5.53 (d, J = 4.1 Hz, 1H, H-1), 5.51 (d, J = 8.4 Hz, 1H, H-3′), 4.67 (dd, J = 11.4, 1.9 Hz, 1H, H-6a), 4.61 (t, J = 8.0 Hz, 1H, H-4′), 4.64–4.47 (m, 2H, H-6′a, H-6′b), 4.32–4.23 (m, 2H, H-6b, H-5), 4.16 (ddd, J = 8.1, 6.2, 4.3 Hz, 1H, H-5′), 3.67 (t, J = 9.4 Hz, 1H, H-3), 3.66 (d, J = 12.3 Hz, 1H, H-1′a), 3.60 (d, J = 12.2 Hz, 1H, H-1′b), 3.48 (dd, J = 9.7, 4.0 Hz, 1H, H-2), 3.32 (t, signal overlapped by CD3OD, H-4). 13C NMR (101 MHz, CD3OD) δ 169.4 (COO), 168.9 (COO), 168.4 (COO), 161.4 (C-Ph), 161.3 (C-Ph), 161.2 (C-Ph), 147.6 (CH-A1), 146.9, 146.8 (CH-A2, CH-A3), 131.5 (2×CH-Ph1) 131.4 (2×CH-Ph3), 131.2 (2×CH-Ph2), 127.2 (C-Ph), 127.1 (2×C-Ph), 116.8 (4×CH-Ph1,2), 116.7 (2×CH-Ph3), 115.0, 114.9, 114.6 (CH-B1, CH-B2, CH-B3), 105.0 (C-2′), 92.6 (C-1), 81.2 (C-5′), 79.1 (C-3′), 75.0 (C-3), 74.7 (C-4′), 73.1 (C-2), 72.3 (C-5), 72.1 (C-4), 65.6 (C-6, C-6′), 65.4 (C-1′). HRMS (ESI): m/z calcd. for C39H40O17 [M + Na]+ = 803.21577, found 803.21580.
- 6,3′,1′,6′-Tetra-O-coumaroyl sucrose (19a, vanicoside D). Amorphous white solid, mp 147.6–154.2 °C [59]; = +25.0° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.72 (d, J = 15.9 Hz, 1H, A1), 7.66 (d, J = 15.9 Hz, 1H, A2), 7.63 (d, J = 16.0 Hz, 1H, A3), 7.61 (d, J = 16.0 Hz, 1H, A4), 7.49 (d, J = 8.8 Hz, 2H, H-Ph), 7.42 (d, J = 8.8 Hz, 2H, H-Ph), 7.41 (d, J = 8.5 Hz, 2H, H-Ph), 7.39 (d, J = 8.5 Hz, 2H, H-Ph), 6.80 (d, J = 8.7 Hz, 2H, H-Ph), 6.78 (d, J = 8.7 Hz, 2H, H-Ph), 6.76 (d, J = 8.6 Hz, 2H, H-Ph), 6.75 (d, J = 8.6 Hz, 2H, H-Ph), 6.44 (d, J = 16.0 Hz, 2H, H-Ph), 6.41 (d, J = 15.9 Hz, 1H, H-B1), 6.35 (d, J = 16.1 Hz, 1H, H-B3), 6.31 (d, J = 16.2 Hz, 1H, H-B2), 5.63 (d, J = 8.6 Hz, 1H, H-B4), 5.63 (d, J = 8.6 Hz, 1H, H-3′), 5.58 (d, J = 3.8 Hz, 1H, H-1), 4.69 (t, J = 8.7 Hz, 1H, H-4′), 4.69 (dd, J = 11.3, 1.5 Hz, 1H, H-6a), 4.62–4.46 (m, 2H, H-6′a, H-6′b), 4.35 (d, J = 12.0 Hz, 1H, H-1′a), 4.32 (d, J = 12.0 Hz, 1H, H-1′b), 4.31–4.24 (m, 1H, H-5), 4.29 (dd, J = 11.0, 8.8 Hz, 1H, H-6a), 4.19 (ddd, J = 9.3, 5.2, 3.0 Hz, 1H, H-5′), 3.66 (t, J = 9.3 Hz, 1H, H-3), 3.47 (dd, J = 9.7, 4.0 Hz, 1H, H-2), 3.34 (t, J = 9.1 Hz, 1H, H-4). HRMS (ESI): m/z calcd. for C48H46O19 [M + Na]+ = 949.25255, found 949.25200.
- 6-O-feruloyl-3′-O-coumaroyl sucrose (15b). White foam, = −54.9° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.9 Hz, 1H, H-A1), 7.62 (d, J = 15.8 Hz, 1H, H-A2), 7.51 (d, J = 8.7 Hz, 2H, H-Cou), 7.22 (d, J = 2.2 Hz, 1H, H-Fer), 7.06 (dd, J = 8.2, 1.9 Hz, 1H, H-Fer), 6.80 (d, J = 8.6 Hz, 2H, H-Cou), 6.79 (d, J = 8.4 Hz, 1H, H-Fer), 6.45 (d, J = 15.9 Hz, 1H, H-B2), 6.42 (d, J = 15.9 Hz, 1H, H-B1), 5.49 (d, J = 7.9 Hz, 1H, H-3′), 5.48 (d, J = 4.3 Hz, 1H, H-1), 4.60 (dd, J = 11.5, 1.4 Hz, 1H, H-6a), 4.46 (t, J = 8.1 Hz, 1H, H-4′), 4.27 (dd, J = 11.4, 6.8 Hz, 1H, H-6b), 4.27–4.18 (m, 1H, H-5), 3.97 (td, J = 7.5, 2.8 Hz, 1H, H-5′), 3.91 (dd, J = 11.8, 7.0 Hz, 1H, H-6′a), 3.87 (s, 3H, OCH3), 3.82 (dd, J = 11.8, 2.9 Hz, 1H, H-6′b), 3.67 (t, J = 9.3 Hz, 1H, H-3), 3.64 (d, J = 12.2 Hz, 1H, H-1′a), 3.59 (d, J = 12.2 Hz, 1H, H-1′b), 3.47 (dd, J = 9.7, 3.8 Hz, 1H, H-2), 3.33 (t, J = 9.4 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.2 (COO), 168.4 (COO), 161.4 (C-Cou), 150.6 (C-Fer), 149.4 (C-Fer), 147.5 (CH-A1), 147.1 (CH-A2), 131.4 (2×CH-Cou), 127.7 (C-Fer), 127.2 (C-Cou), 124.3 (CH-Fer), 116.8 (2×CH-Cou), 116.4 (CH-Fer), 115.4 (CH-B2), 114.7 (CH-B1), 111.6 (CH-Fer), 104.8 (C-2′), 92.8 (H-1), 84.2 (C-5′), 79.4 (C-3′), 75.0 (C-3), 74.2 (C-4′), 73.1 (C-2), 72.3 (C-5), 71.9 (C-4), 65.5 (C-1′), 65.4 (C-6), 63.9 (C-6′), 56.5 (OCH3). HRMS (ESI): m/z calcd. for C31H36O16 [M + Na]+ = 687.18956, found 687.18949.
- 3′-O-coumaroyl-6′-O-feruloyl sucrose (16b). NMR data extracted from the mixture with 15b (reaction with Pentopan, Table 3, entry 5); 1H NMR (400 MHz, CD3OD) δ 7.72 (d, J = 15.8 Hz, 1H, H-A1), 7.66 (d, J = 15.9 Hz, 1H, H-A2), 7.50 (d, J = 8.8 Hz, 2H, H-Cou), 7.18 (d, J = 2.0 Hz, 1H, H-Fer), 7.09 (dd, J = 8.2, 1.9 Hz, 1H, H-Fer), 6.82 (d, J = 8.2 Hz, 2H, H-Fer), 6.81 (d, J = 8.8 Hz, 1H, H-Cou), 6.41 (d, J = 16.0 Hz, 1H, H-B1), 6.40 (d, J = 15.9 Hz, 1H, H-B2), 5.49 (d, J = 8.0 Hz, 1H, H-3′), 5.45 (d, J = 3.7 Hz, 1H, H-1), 4.57 (dd, J = 11.7, 7.4 Hz, 1H, H-6′a), 4.51 (dd, J = 11.8, 3.7 Hz, H-6′b), 4.45 (t, J = 7.9 Hz, 1H, H-4′), 4.18 (td, J = 7.7, 3.9 Hz, 1H, H-5′), 3.97 (dt, J = 7.7, 3.6 Hz, 1H, H-5), 3.92 (bd, J = 10.4 Hz, 1H, H-6a), 3.82–3.78 (m, 1H, H-6b), 3.89 (s, 3H, OCH3), 3.68 (t, J = 9.4 Hz, 1H, H-3), 3.67 (d, J = 12.5 Hz, 1H, H-1′a), 3.61 (d, J = 12.4 Hz, 1H, H-1′b), 3.44 (dd, J = 9.7, 3.7 Hz, 1H, H-2), 3.41 (t, J = 9.4 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.0 (COO), 168.3 (COO), 161.3 (C-Cou), 150.6 (C-Fer), 149.3 (C-Fer), 147.5 (CH-A1), 147.2 (CH-A2), 131.4 (2×CH-Cou), 127.7 (C-Fer), 127.1 (C-Cou), 124.2 (CH-Fer), 116.8 (2×CH-Cou), 116.5 (CH-Fer), 115.2 (CH-B2), 114.6 (CH-B1), 111.7 (CH-Fer), 105.1 (C-2′), 93.1 (H-1), 81.2 (C-5′), 79.3 (C-3′), 2×75.0 (C-3, C-4′), 74.4 (C-5), 73.2 (C-2), 71.4 (C-4), 66.3 (C-6′), 65.1 (C-1′), 62.6 (C-6), 56.5 (OCH3).
- 6,4′-di-O-feruloyl-3′-O-coumaroyl sucrose (17b). NMR data extracted from the fraction with 15b (reaction with Lipozyme, Table 3, entry 4). 1H NMR (400 MHz, CD3OD) δ 7.71 (d, J = 15.8 Hz, 1H, H-A), 7.60 (d, J = 15.9 Hz, 1H, H-2), 7.56 (d, J = 15.8 Hz, 1H, H-3), 7.50 (d, J = 8.6 Hz, 2H, H-Cou), 7.13 (d, J = 2.0 Hz, 1H, H-Fer1), 7.09 (d, J = 2.0 Hz, 1H, H-Fer2), 7.03 (dd, J = 8.4, 2.2 Hz, 1H, H-Fer1), 7.01 (dd, J = 8.4, 2.2 Hz, 1H, H-Fer2), 6.79 (d, J = 8.1 Hz, 1H, H-Fer2), 6.79 (d, J = 8.7 Hz, 2H, H-Cou), 6.70 (d, J = 8.1 Hz, 1H), 6.49 (d, J = 15.4 Hz, 1H, H-B2), 6.41 (d, J = 15.8 Hz, 1H, H-B1), 6.29 (d, J = 15.9 Hz, 1H, H-B3), 5.82 (d, J = 7.6 Hz, 1H, H-3′), 5.68 (t, J = 7.5 Hz, 1H, H-4′), 5.53 (d, J = 3.6 Hz, 1H, H-1), 4.68 (bd, J = 10.9 Hz, 1H, H-6a), 4.35–4.28 (m, 1H, C-5), 4.29–4.24 (m, 1H, H-6b), 4.24–4.17 (m, 1H, H-5′), 4.01 (dd, J = 12.1, 7.2 Hz, 1H, H-6′a), 3.90 (dd, J = 12.0, 3.7, 1H, H-6′b), 3.87 (s, 3H, OCH3), 3.80 (s, 3H, OCH3), 3.71 (t, J = 9.4 Hz, 1H, H-3), 3.67 (d, J = 12.4 Hz, 1H, H-1′a), 3.63 (d, J = 12.2 Hz, 1H, H-1′b), 3.51 (dd, J = 9.8, 3.8 Hz, 1H, H-2), 3.32 (t, J = 9.7 Hz, 1H, H-4). 13C NMR (101 MHz, MeOD) δ 169.4 (COO), 168.2 (COO), 168.0 (COO), 161.4 (C-Cou), 150.8 (C-Fer1), 150.5 (C-Fer2), 149.3 (C-Fer1), 149.2 (C-Fer2), 148.0 (CH-A3), 147.9 (CH-A1), 146.9 (C-A2), 131.5 (2×CH-Cou), 127.8 (C-Fer), 127.5 (C-Fer), 127.1 (C-Cou), 124.4 (CH-Fer2), 124.2 (CH-Fer1), 116.8 (2×CH-Cou), 116.5 (CH-Fer2), 116.4 (CH-Fer1), 115.6 (CH-B2), 114.4 (CH-B1), 114.3 (CH-B3), 111.9 (CH-Fer1), 111.8 (CH-Fer2), 105.3 (C-2′), 93.1 (C-1), 82.9 (C-5′), 77.1 (C-3′), 76.4 (C-4′), 74.9 (C-3), 73.0 (C-2), 72.8 (C-5), 72.0 (C-4), 65.7 (C-6), 65.0 (C-1′), 64.1 (C-6′), 56.5 (2×OCH3).
- 6,6′-Di-O-feruloyl-3′-O-coumaroyl sucrose (18b). White foam, = −15.0° (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.72 (d, J = 15.9 Hz, 1H, H-A1)), 7.60 (d, J = 15.9 Hz, 1H, H-A2), 7.57 (d, J = 16.0 Hz, 1H, H-A3), 7.51 (d, J = 8.7 Hz, 2H, H-Cou), 7.19 (d, J = 1.9 Hz, 1H, H-Fer1), 7.08 (d, J = 1.9 Hz, 1H, H-Fer2), 6.99 (dd, J = 8.3, 2.0 Hz, 1H, H-Fer1), 6.98 (dd, J = 8.3, 2.0 Hz, 1H, H-Fer2), 6.80 (d, J = 9.0 Hz, 2H, H-Cou), 6.78 (d, J = 8.7 Hz, 1H, H-Fer2), 6.74 (d, J = 8.1 Hz, 1H, H-Fer1), 6.46 (d, J = 15.8 Hz, 1H, H-B2), 6.43 (d, J = 15.9 Hz, 1H, H-B1), 6.28 (d, J = 15.9 Hz, 1H, H-B3), 5.52 (d, J = 8.1 Hz, 1H, H-3′), 5.52 (d, J = 4.2 Hz, 1H, H-1), 4.70 (dd, J = 11.5, 1.5 Hz, 1H, H-6a), 4.64 (t, J = 8.2 Hz, 1H, H-4′), 4.60 (dd, J = 11.9, 4.1 Hz, 1H, H-6′a), 4.52 (dd, J = 11.9, 6.5 Hz, 1H, 6′b), 4.35–4.24 (m, 1H, H-5), 4.22 (dd, J = 7.5, 11.6 Hz, 1H, H-6b), 4.17 (ddd, J = 8.1, 6.5, 4.1 Hz, 1H, H-5′), 3.87 (s, 3H, OCH3), 3.84 (s, 3H, OCH3), 3.67 (t, J = 9.3 Hz, 1H, H-3), 3.65 (d, J = 12.1 Hz, 1H, H-1′a), 3.60 (d, J = 12.2 Hz, 1H, H-1′b), 3.47 (dd, J = 9.8, 3.8 Hz, 1H, H-2), 3.29 (dd, J = 9.9, 9.0 Hz, 1H, H-4). 13C NMR (101 MHz, CD3OD) δ 169.3 (COO), 168.8 (COO), 168.4 (COO), 161.4 (C-Cou), 150.6 (C-Fer1), 150.6 (C-Fer2), 149.3 (C-Fer1), 149.3 (C-Fer2), 147.6 (CH-A1), 147.2 (CH-A2), 147.0 (CH-A3), 131.5 (2×CH-Cou), 127.7 (C-Fer1), 127.7 (C-Fer2), 127.2 (C-Cou), 124.5 (CH-Fer1), 124.1 (CH-Fer2), 116.8 (2×CH-Cou), 116.5 (CH-Fer2), 116.3 (CH-Fer1), 115.3 (CH-B2), 115.2 (CH-B3), 114.6 (CH-B1), 111.7 (CH-Fer2), 111.6 (CH-Fer2), 104.9 (C-2′), 92.6 (C-1), 81.2 (C-5′), 79.1 (C-3′), 75.0 (C-3), 74.7 (C-4′), 73.1 (C-2), 72.4 (C-5), 72.2 (C-4), 65.8 (C-6), 65.7 (C-6′), 65.5 (C-1′), 56.5 (OCH3), 56.4 (OCH3). HRMS (ESI): m/z calcd. for C41H44O19 [M + Na]+ = 863.23690, found 893.23625.
- 6,3′-Di-O-(3,4,5-tri-O-methoxycinnamoyl) sucrose (15c, glomeratose D). White solid, m.p. = 101–103 °C; = −49.7° (c 1.0, MeOH), = −55.8° (c 0.53, MeOH) [57]. 1H NMR (400 MHz, CD3OD) δ 7.69 (d, J = 16.0 Hz, 1H, H-A1), 7.61 (d, J = 15.9 Hz, 1H, H-A2), 6.95 (s, 2H, H-Ph1), 6.91 (s, 2H, H-Ph2), 6.55 (d, J = 16.0 Hz, 1H, H-B2), 6.54 (d, J = 15.7 Hz, 1H, H-B1), 5.53 (d, J = 8.0 Hz, 1H, H-3′), 5.52 (d, J = 3.8 Hz, 1H, H-1), 4.71 (d, J = 11.6, 1.6 Hz, 1H, H-6a), 4.51 (t, J = 8.0 Hz, 1H, H-4′), 4.32–4.26 (m, 1H, H-5), 4.21 (d, J = 11.5, 7.4 Hz 1H, H-6b), 3.98 (ddd, J = 8.1, 6.8, 3.2 Hz, 1H, H-5′), 3.87 (s, 6H, 2×m-OCH3), 3.85 (s, 6H, 2×m-OCH3), 3.92–3.80 (m, 2H, H-6′a, H-6′b, overlapped by OCH3 groups), 3.79 (s, 3H, p-OCH3), 3.78 (s, 3H, p-OCH3), 3.67 (dd, J = 9.7, 8.8 Hz, 1H, H-3), 3.63 (d, J = 12.1 Hz, 1H, H-1′a), 3.58 (d, J = 12.2 Hz, 1H, H-1′b), 3.48 (dd, J = 9.6, 4.0 Hz, 1H, H-2), 3.31 (t, J = 9.6 Hz, 1H, H-4, overlapped by CD3OD). 13C NMR (101 MHz, CD3OD) δ 168.6 (COO), 167.8 (COO), 154.8 (2×C-Ph1), 154.7 (2×C-Ph2), 147.2 (C-A1), 146.6 (C-A2), 141.3 (C-Ph1), 141.2 (C-Ph2), 131.5 (C-Ph1) 131.5 (C-Ph2), 118.1 (CH-B1), 117.8 (CH-B2), 106.9 (2×CH-Ph1), 106.8 (2×CH-Ph2), 104.8 (C-2′), 92.7 (C-1), 84.3 (C-5′), 79.4 (C-3′), 75.1 (C-3), 74.2 (C-4′), 73.1 (C-2), 72.5 (C-5), 72.0 (C-4), 65.8, 65.7 (C-1′, C-6), 63.8 (C-6′), 61.2 (p-OCH3), 61.1 (p-OCH3), 56.8 (2×m-OCH3), 56.7 (2×m-OCH3). HRMS (ESI): m/z calcd. for C36H46O19 [M + Na]+ = 805.25255; found 805.25299.
- 6,3′,4′-Di-O-(3,4,5-tri-O-methoxycinnamoyl) sucrose (16c). Selected signals from impurity below 5% in fraction of 17c. 1H NMR (400 MHz, CD3OD) δ 5.86 (d, J = 7.5 Hz, 1H), 5.73 (t, J = 7.5 Hz, 1H), 5.57 (d, J = 3.9 Hz, 1H).
- 6,3′,6′-Tri-O-(3,4,5-tri-O-methoxycinnamoyl) sucrose (17c). White solid; = −10.0° (c 1.0, CH3OH) 1H NMR (400 MHz, CD3OD) δ 7.70 (d, J = 15.9 Hz, 1H, H-A1), 7.57 (d, J = 16.1 Hz, 1H, H-A2), 7.53 (d, J = 16.1 Hz, 1H, H-A3), 6.95 (s, 2H, H-Ph1), 6.84 (s, 2H, H-Ph2), 6.78 (s, 2H, H-Ph3), 6.55 (d, J = 16.0 Hz, 1H, H-B1), 6.54 (d, J = 15.9 Hz, 1H, H-B2), 6.37 (d, J = 15.9 Hz, 1H, H-B3), 5.56 (d, J = 7.8 Hz, 1H, H-3′), 5.53 (d, J = 3.9 Hz, 1H, H-1), 4.79 (dd, J = 11.8, 1.7 Hz, 1H, H-6a), 4.68 (t, J = 7.9 Hz, 1H, H-4′), 4.62 (dd, J = 11.9, 4.3 Hz, 1H, H-6′a), 4.53 (dd, J = 11.9, 6.5 Hz, 1H, H-6′b), 4.35 (ddd, J = 10.1, 8.1, 1.7 Hz, 1H, H-5), 4.20 (ddd, J = 10.0, 6.4, 4.2 Hz, 1H, H-5′), 4.17 (dd, J = 11.9, 8.1 Hz, 1H, H-6b), 3.86 (s, 6H, 2×m-OCH3), 3.83 (s, 6H, 2×m-OCH3), 3.79 (s, 6H, m-OCH3), 3.78 (s, 3H, p-OCH3), 3.77 (s, 3H, p-OCH3), 3.72 (s, 3H, p-OCH3), 3.68 (dd, J = 9.8, 8.8 Hz, 1H, H-3), 3.65 (d, J = 12.2 Hz, 1H, H-1′a), 3.60 (d, J = 12.3 Hz, 1H, H-1′b), 3.49 (dd, J = 9.7, 3.9 Hz, 1H, H-2), 3.27 (dd, J = 10.1, 8.8 Hz, 1H, H-4). HRMS (ESI): m/z calcd. for C48H58O23 [M + Na]+ = 1025.32611, found 1025.32666.
- 2,6-Di-O-(3,4,5-tri-O-methoxycinnamoyl) sucrose (20). White amorphous solid, t.t. = 171–174 C; = + 28.0° (c 0.5, MeOH); 1H NMR (400 MHz, CD3OD) δ 7.74 (d, J = 15.9 Hz, 1H, H-A1), 7.67 (d, J = 16.0 Hz, 1H, H-A2), 6.98 (s, 2H, H-Ph1), 6.95 (s, 2H, H-Ph2), 6.58 (d, J = 15.9 Hz, 1H, H-B2), 6.54 (d, J = 16.0 Hz, 1H, H-B1), 5.62 (d, J = 3.8 Hz, 1H, H-1), 4.75 (dd, J = 10.1, 3.7 Hz, 1H, H-2), 4.56 (dd, J = 11.9, 1.8 Hz, 1H, H-6a), 4.32 (dd, J = 11.8, 6.6 Hz, 1H, H-6b), 4.22 (d, J = 8.8 Hz, 1H, H-3′), 4.23–4.19 (m, 1H, H-5), 4.08 (t, J = 8.7 Hz, 1H, H-4′), 4.02 (dd, J = 10.1, 8.9 Hz, 1H, H-3), 3.88 (s, 6H, m-OCH3), 3.88 (s, 6H, m-OCH3), 3.87–3.81 (m, 2H, H-6′a, H-5′, overlapped with signals of OCH3), 3.80 (s, 3H, p-OCH3), 3.80 (s, 3H, p-OCH3), 3.76 (dd, J = 12.1, 6.2 Hz, 1H, 6′b), 3.53 (d, J = 11.9 Hz, 1H, H-1′a), 3.45 (dd, J = 10.1, 8.9 Hz, 1H, H-4), 3.32 (d, J = 11.9 Hz, 1H, H-1′b). 13C NMR (101 MHz, CD3OD) δ 168.6 (COO), 168.3 (COO), 154.9 (2×C-Ph1), 154.8 (2×C-Ph2), 147.2 (C-A1), 146.6 (C-A2), 141.5 (C-Ph1), 141.3 (C-Ph2), 131.6 (C-Ph1) 131.5 (C-Ph2), 118.1 (CH-B2), 117.9 (CH-B1), 106.9 (2×CH-Ph1), 106.8 (2×CH-Ph2), 105.7 (C-2′), 90.5 (C-1), 84.0 (C-5′), 77.1 (C-3′), 75.7 (C-4′), 74.6 (C-2), 72.1 (C-4), 72.0 (C-3), 71.9 (C-5), 65.3 (C-6), 64.2 (C-6′), 63.1 (C-1′), 61.2 (2×p-OCH3), 56.8 (4xm-OCH3). HRMS (ESI): m/z calcd. for C36H46O19 [M + Na]+ = 805.25255; found 805.25263.
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Entry | Enzyme | Donor | Solvent | Time (days) | Product | Yield (%) |
---|---|---|---|---|---|---|
1 | LPZ | 5a | CH3CN | 7 | n.d. | - |
2 | LPZ | 5b | t-BuOH | 7 | n.d. | - |
3 | LPZ | 5b | CH3CN | 30 | n.d. | - |
4 | LPZ | 5c | CH3CN | 20 | n.d. | - |
5 | PT | 5a | CH3CN | 62 | 9a | 41 |
6 | PT | 5b | CH3CN | 59 | 9b | 44 |
7 | PT | 5c | CH3CN | 72 | n.d. | - |
Entry | Enzyme | Donor | Solvent | Time (h) | Acylated Products/Yields (%) | |||||
---|---|---|---|---|---|---|---|---|---|---|
10a | 11a | 12a | 13a | 14a | Triacyls 1 | |||||
1 | LPZ | 5a | CH3CN | 120 | 30 | 5 | 13 | 12 | 12 | 7 1 |
2 | LPZ | 5a | MeTHF | 116 | 32 | 4 | 19 | 7 | 12 | 4 1 |
3 | PT | 5a | CH3CN | 129 2 | 19 | n.d. | 14 | n.d | 3 | n.d |
10b | 11b | 12b | 13b | 14b | ||||||
4 | LPZ | 5b | CH3CN | 114 | 31 | 3 | 18 | 4 | 4 | traces |
5 | LPZ | 5b | MeTHF | 108 | 29 | 4 | 18 | 5 | 7 | n.d |
6 | PT | 5b | CH3CN | 68 2 | 25 | n.d. | 23 | n.d | 10 | n.d |
7 | PT | 5b | MeTHF | 153 2 | n.d | n.d | n.d | n.d | n.d | n.d |
Entry | Enzyme | Acceptor/Donor | Solvent | Time (h) | Acylated Products /Yields (%) | ||||
---|---|---|---|---|---|---|---|---|---|
15a | 16a | 17a | 18a | Tetraacyls | |||||
1 | LPZ | 4a/5a | CH3CN | 112 | 65 | n.d. | 22 (1:4) | traces | |
2 | LPZ | 4a/5a | MeTHF | 65 | 24 | n.d. | 16 | 49 | 2 1 + 7 (19a) |
3 | PT | 4a/5a | CH3CN | 71 3 | 43 (1:1) | n.d. | 6 | n.d. | |
15b | 16b | 17b | 18b | ||||||
4 | LPZ | 4a/5b | CH3CN | 163 | 63 | n.d. | 13 (1:5) | n.d. | |
5 | PT | 4a/5b | CH3CN | 71 3 | 77 (1:1) | n.d. | 16 | n.d. | |
6 | PT | 4a/5b | MeTHF | 120 3 | n.d. | n.d. | n.d. | n.d. | n.d. |
15c | 16c | 17c | 18c | ||||||
7 | LPZ | 4b/5c | CH3CN | 105 | 56 | n.d. | traces | 16 | n.d. |
8 | LPZ | 4b/5c | t-AmOH | 72 | 48 2 | n.d. | n.d. | 8 | n.d. |
9 | PP | 4b/5c | CH3CN | 63 3 | n.d. | n.d. | n.d. | n.d. | n.d. |
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Cvečko, M.; Mastihuba, V.; Mastihubová, M. An Exploratory Study of the Enzymatic Hydroxycinnamoylation of Sucrose and Its Derivatives. Molecules 2024, 29, 4067. https://doi.org/10.3390/molecules29174067
Cvečko M, Mastihuba V, Mastihubová M. An Exploratory Study of the Enzymatic Hydroxycinnamoylation of Sucrose and Its Derivatives. Molecules. 2024; 29(17):4067. https://doi.org/10.3390/molecules29174067
Chicago/Turabian StyleCvečko, Matej, Vladimír Mastihuba, and Mária Mastihubová. 2024. "An Exploratory Study of the Enzymatic Hydroxycinnamoylation of Sucrose and Its Derivatives" Molecules 29, no. 17: 4067. https://doi.org/10.3390/molecules29174067