Azidotrimethylsilane → HCID 101715677, compound

HRID 576499Notes

Reaction equation

[CH2:1]([O:4][C:5]1[C:6]2[N:7]=[CH:8][N:9]([C:32]=2[N:33]=[C:34]([NH2:36])[N:35]=1)[C@@H:10]1[O:31][C@H:21]([CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[C@@H:12]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[CH2:11]1)[CH:2]=[CH2:3].[Si]([N:41]=[N+:42]=[N-])(C)(C)C>>[CH2:1]([O:4][C:5]1[C:6]2[N:7]=[CH:8][N:9]([C:32]=2[N:33]=[C:34]([N:36]=[N+:41]=[N-:42])[N:35]=1)[C@@H:10]1[O:31][C@H:21]([CH2:22][O:23][Si:24]([C:27]([CH3:28])([CH3:29])[CH3:30])([CH3:26])[CH3:25])[C@@H:12]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:15])[CH3:16])[CH2:11]1)[CH:2]=[CH2:3]

Participants

Reactant 2

HCID 78378Azidotrimethylsilane

HCID 10673907HCID 10673907, compound

Product 1

HCID 101715677HCID 101715677, compoundYield 63%

Procedure

As described for the synthesis of 2a, this compound was prepared by a reaction 1b (3.0 g, 5.6 mmol) with TMS—N3 (10 molar equiv) and t-BuONO (10 molar equiv). Chromatographic purification of the crude material on a silica gel column using 20% EtOAc in hexanes afforded 1.98 g (63% yield) of 2b as a viscous, yellow oil. Rf(SiO2/30% EtOAc in hexanes)=0.63. IR (neat): 2956, 2930, 2857, 2130, 1600 cm−1. 1H NMR (CDCl3): δ 8.18 (s, 1H, Ar—H), 6.42 (t, 1H, H-1′, J=6.4 Hz), 6.18-6.11 (m, 1H, ═CH), 5.49 (dd, 1H, ═CHtrans, J=1.4, 17.2 Hz), 5.33 (dd, 1H, ═CHcis, J=1.4, 10.2 Hz), 5.11 (d, 2H, OCH2, J=5.8 Hz), 4.61-4.59 (m, 1H, H-3′), 4.01 (app q, 1H, H-4′, Japp˜3.4 Hz), 3.88 (dd, 1H, H-5′, J=4.0, 10.2 Hz), 3.79 (dd, 1H, H-5′, J=3.0, 10.2 Hz), 2.56 (app quint, 1H, H-2′, Japp˜6.5 Hz), 2.43 (ddd, 1H, H-2′, J=3.9, 5.9, 10.3 Hz), 0.93 and 0.92 (2s, 18H, t-Bu), 0.11 (s, 12H, SiCH3). Resonances of the tetrazolyl form (<5%): δ 8.25 (s, 1H, Ar—H), 4.64-4.63 (m, 1H, H-3′), 2.64-2.62 (m, 1H, H-2′). 13C NMR (CDCl3): δ 161.0, 155.8, 153.0, 140.6, 132.1, 119.3, 88.1, 84.5, 71.9, 68.6, 68.2, 62.9, 41.6, 26.1, 25.9, 18.5, 18.1, −4.4, −4.6, −5.3. 1H NMR (DMSO-d6): δ 8.47 (s, 1H, Ar—H), 6.32 (t, 1H, H-1′, J=6.4 Hz), 6.16-6.09 (m, 1H, ═CH), 5.46 (d, 1H, ═CHtrans, J=18.0 Hz), 5.33 (d, 1H, ═CHcis, J=10.7 Hz), 5.07 (d, 2H, OCH2, J=5.4 Hz), 4.62 (m, 1H, H-3′), 3.58 (d, 1H, H-4′, J=4.0 Hz), 3.78 (dd, 1H, H-5′, J=5.9, 11.2 Hz), 3.67 (dd, 1H, H-5′, J=4.4, 11.2 Hz), 2.90 (app quint, 1H, H-2′, Japp˜6.5 Hz), 2.34 (dd, 1H, H-2′, J=5.2, 11.2 Hz), 0.93 and 0.83 (2s, 18H, t-Bu), 0.12, 0.01, and 0.0.1 (3s, 12H, SiCH3). Resonances of the tetrazolyl form (<10%): δ 8.57 (s, 1H, Ar—H), 4.70 (m, 1H, H-3′), 0.81 (s, 18H, t-Bu), 0.13, 0.04, and −0.03 (3s, 12H, SiCH3). HRMS calculated for C25H43N7O4Si2Na [M+Na]+: 584.2807 found: 584.2818.

Workup

customChromatographic purification of the crude material on a silica gel column

Sources & evidence

ORD record: ord-b060d46f3f994eb9947f2073a99a55a3
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09040498B2

Reaction notes

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