Methanesulfonyl chloride → (1-Azido-3-methylbutyl)(3-Buten-1-yl)diphenylsilane

HRID 8542Notes

Reaction equation

HRID 8542 reaction equation
[CH2:1]([Si:5]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH:6](O)[CH2:7][CH:8]([CH3:10])[CH3:9])[CH2:2][CH:3]=[CH2:4].CS(Cl)(=O)=O.[N-:29]=[N+:30]=[N-:31].[Na+]>C(Cl)Cl.CCN(CC)CC>[N:29]([CH:6]([Si:5]([CH2:1][CH2:2][CH:3]=[CH2:4])([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[CH2:7][CH:8]([CH3:9])[CH3:10])=[N+:30]=[N-:31]

Participants

6

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 33557Sodium AzideHCID 220158361-[(3-Buten-1-yl)diphenylsilyl]-3-methyl-1-butanol

Product 1

HCID 22015837(1-Azido-3-methylbutyl)(3-Buten-1-yl)diphenylsilaneYield 87%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of 34 (1.68 g, 5.16 mmol) in CH2Cl2 (100 mL) and Et3N (3.6 mL) at 0° C. was added dropwise over 5 min methanesulfonyl chloride (2.96 g, 25.8 mmol), and the solution was allowed to warm to rt over 1 h. After stirring overnight under argon, the mixture was cooled to 0° C. and quenched with water (50 mL). The organic layer was isolated and the aqueous layer extracted twice with 20-mL portions of CH2Cl2. The combined organic extracts were concentrated in vacuo at rt. The crude mesylate was dissolved in DMF (100 mL), and to this solution was added sodium azide (1.68 g, 25.8 mmol). After stirring for 8 h at rt, the mixture was partitioned between water (200 mL) and EtOAc (200 mL). The organic layer was isolated and aqueous layer extracted twice with 50-mL portions of EtOAc. The combined organic extracts were washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated. Flash chromatography over silica gel (1/9 EtOAc:hexane) gave pure 35 as a colorless oil (1.57 g, 87%): Rf=0.90 (1/9 EtOAc:hexane); 1H NMR (300 MHz, CDCl3) δ 7.57 (d, J=6.7 Hz, 4H), 7.41 (m, 6H), 5.88 (m, 1H), 5.00 (dd, J=17.0, 1.5 Hz, 1H), 4.92 (dd, J=10.2, 1.5 Hz, 1H), 3.44 (d, J=12.4 Hz, 1H), 2.12 (m, 2H), 1.84 (m, 1H), 1.60 (t, J=12.5 Hz, 1H), 1.30 (m, 3H), 0.92 (d, J=6.7 Hz, 3H), 0.89 (d, J=6.7 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 140.7, 135.3, 132.6, 129.9, 128.0, 113.3, 49.2, 38.8, 27.5, 25.9, 23.3, 20.7, 10.5; IR (neat) 3071 (w), 3051 (w), 2995 (w), 2957 (s), 2923 (m), 2866 (m), 2102 (s), 1642 (w), 1473 (w), 1432 (s), 1264 (m), 1188 (w), 1116 (s), 1004 (w), 915 (m), 743 (s), 701 (s) cm−1; MS (FAB) m/e (rel. intensity) 350 (MH+, 18), 323 (32), 322 (100), 321 (27), 320 (16), 315 (42), 306 (42), 252 (17), 251 (23), 237 (18), 236 (73), 223 (26), 208 (17); HRMS (FAB) calcd for C11H28N3Si: 350.2053, found: 350.2040. Anal. Calcd for C21H27N3Si: C, 72.16; H, 7.79; N, 12.02. Found: C, 71.99; H, 7.91; N, 11.60.

Workup

  1. temperaturethe mixture was cooled to 0° C.
  2. customquenched with water (50 mL)
  3. customThe organic layer was isolated
  4. extractionthe aqueous layer extracted twice with 20-mL portions of CH2Cl2
  5. concentrationThe combined organic extracts were concentrated in vacuo at rt
  6. dissolutionThe crude mesylate was dissolved in DMF (100 mL)
  7. stirringAfter stirring for 8 h at rt
  8. customthe mixture was partitioned between water (200 mL) and EtOAc (200 mL)
  9. customThe organic layer was isolated
  10. extractionaqueous layer extracted twice with 50-mL portions of EtOAc
  11. washThe combined organic extracts were washed with saturated aqueous NaCl
  12. dry with materialdried over Na2SO4
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-0c1116db73674a7c866544136f11b01a
Source dataset
uspto-grants-2006_08
Patent number
US07087776B2

Reaction notes

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