Reaction SMILES: CS(C)=O.C(Cl)(=O)C(Cl)=O.N#N.C(Cl)(Cl)Cl.[CH2:17]([O:55][CH:56]1[C@H:60]2[C@H:61]([O:81][Si:82]([C:85]([CH3:88])([CH3:87])[CH3:86])([CH3:84])[CH3:83])[N:62]([C:73]([O:75][CH2:76][C:77]([Cl:80])([Cl:79])[Cl:78])=[O:74])[C:63]3[CH:70]=[CH:69][C:68]([O:71][CH3:72])=[CH:67][C:64]=3[C:65](=[O:66])[N:59]2[CH2:58][C@H:57]1[OH:89])[CH2:18][CH2:19][O:20][CH:21]1[C@H:25]2[C@H:26]([O:46][Si:47]([C:50]([CH3:53])([CH3:52])[CH3:51])([CH3:49])[CH3:48])[N:27]([C:38]([O:40][CH2:41][C:42]([Cl:45])([Cl:44])[Cl:43])=[O:39])[C:28]3[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][C:29]=3[C:30](=[O:31])[N:24]2[CH2:23][C@H:22]1[OH:54]>C(Cl)Cl>[CH2:19]([O:20][CH:21]1[C@H:25]2[C@H:26]([O:46][Si:47]([C:50]([CH3:53])([CH3:52])[CH3:51])([CH3:49])[CH3:48])[N:27]([C:38]([O:40][CH2:41][C:42]([Cl:45])([Cl:44])[Cl:43])=[O:39])[C:28]3[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][C:29]=3[C:30](=[O:31])[N:24]2[CH2:23][C:22]1=[O:54])[CH2:18][CH2:17][O:55][CH:56]1[C@H:60]2[C@H:61]([O:81][Si:82]([C:85]([CH3:86])([CH3:87])[CH3:88])([CH3:83])[CH3:84])[N:62]([C:73]([O:75][CH2:76][C:77]([Cl:80])([Cl:79])[Cl:78])=[O:74])[C:63]3[CH:70]=[CH:69][C:68]([O:71][CH3:72])=[CH:67][C:64]=3[C:65](=[O:66])[N:59]2[CH2:58][C:57]1=[O:89]
Reactant: COc1ccc2c(c1)C(=O)N1C[C@@H](O)C(OCCCOC3[C@H](O)CN4C(=O)c5cc(OC)ccc5N(C(=O)OCC(Cl)(Cl)Cl)[C@@H](O[Si](C)(C)C(C)(C)C)[C@H]34)[C@H]1[C@H](O[Si](C)(C)C(C)(C)C)N2C(=O)OCC(Cl)(Cl)Cl
Agent: N#N
Agent: O=C(Cl)C(=O)Cl
Solvent: CS(C)=O
Solvent: ClCCl
Solvent: ClC(Cl)Cl
Product: COc1ccc2c(c1)C(=O)N1CC(=O)C(OCCCOC3C(=O)CN4C(=O)c5cc(OC)ccc5N(C(=O)OCC(Cl)(Cl)Cl)[C@@H](O[Si](C)(C)C(C)(C)C)[C@H]34)[C@H]1[C@H](O[Si](C)(C)C(C)(C)C)N2C(=O)OCC(Cl)(Cl)Cl
Temperature: -55 °C
Reaction time: 1.5 h
Yield: 71.8 %

Procedure:
A solution of anhydrous DMSO (0.82 mL, 0.90 g, 11.5 mmol, 6.0 eg) in dry DCM (20 mL) was added dropwise to a stirred solution of oxalyl chloride (2.88 mL of a 2 M solution in DAM, 5.76 mmol, 3.0 eq) under a nitrogen atmosphere at −60° C. (liq N2/CHCl3). After stirring at −55° C. for 1.5 h, a solution of the substrate 11 (2.26 g, 1.92 mmol) in dry DCM (30 mL) was added dropwise to the reaction mixture, which was then stirred for a further 2 h at −45° C. A solution of TEA (10.8 mL, 7.82 g; 71.7 mmol, 4.2 eq) in dry DCM (90 mL) was added dropwise to the mixture and stirred for a further 30 min. The reaction mixture was left to warm to 0° C., washed with cold 1 N HCl (2×50 mL), H2O (50 mL), brine (50 mL) and dried (MgSO4). Filtration and evaporation of the solvent in vacuo afforded the crude product which was purified by flash column chromatography (70:30 v/v hexane/EtOAc then gradient to 40:60 v/v hexane/EtOAc) to afford carbinolamine 12 as a white glass (1.62 g, 72%): 1H NMR (400 MHz, CDCl3) δ 7.02 (s, 2H, H6), 6.54 (s, 2H, H9), 5.59 (d, 2H, J=9.2 Hz, H11), 4.98 (d, 2H, J=12.0 Hz, Troc CH2), 4.09-3.86 (m, 8H, OCH2CH2CH2O, Troc CH2 and H3), 3.75-3.66 (m, 10H, OCH3×2, H11a, and H3), 2.72 (dd, 2H, J=10.2, 19.6 Hz, H1), 2.82 (dd, 2H, J=2.6, 19.6 Hz, H1), 2.22-2.19 (m, 2H, OCH2CH2CH2O), 0.63 (s, 18H, TBS CH3×6), 0.00 (s×2, 12H, TBS CH3×4); 13C NMR (100.6 MHz, CDCl3) δ 207.7 (C2), 168.0 (Cquat), 153.7 (Cquat), 150.7 (Cquat), 149.4 (Cquat), 127.8 (Cquat), 124.6 (Cquat), 114.0 (C9), 110.6 (C6), 95.1 (Troc CCl3), 87.4 (C11), 74.8 (Troc CH2), 65.0 (OCH2CH2CH2O), 58.9 (C11a), 56.1 (OCH3), 53.0 (C3), 40.3 (C1), 28.8 (OCH2CH2CH2O), 25.6 (TBS CH3), 17.8 (TBS Cquat); MS (ES), m/z (relative intensity) 1224 ([M+48]+., 100), 1210 ([M+34]+., 60), 1199 ([M+Na]+., 35), 1192 ([M+16]+., 40), 1176 (M+., 18).