Nitrogen → HCID 10862346, compound

HRID 362174Notes

Reaction equation

HRID 362174 reaction equation
[C:1]([O:4][C@:5]1([O:21][C@H:20]([C@@H:22]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[O:23][C:24](=[O:26])[CH3:25])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[CH2:9]1)C(O)=O)(=[O:3])[CH3:2].OSN1C=CC=CC1=O.N#N>C1(C)C=CC=CC=1.CN(C1C=CN=CC=1)C.N1C=CC=CC=1.[W]>[C:1]([O:4][C@@H:5]1[O:21][C@H:20]([C@@H:22]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[O:23][C:24](=[O:26])[CH3:25])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[CH2:9]1)(=[O:3])[CH3:2]

Participants

8

Reactant 3

HCID 947NitrogenHCID 10874012HCID 10874012, compoundHCID 18465619HCID 18465619, compound

Product 1

HCID 10862346HCID 10862346, compoundYield 68.3%

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 23964TungstenCatalystHCID 1049PyridineSolventHCID 1140TolueneSolvent2×

Procedure

To a solution of acid chloride prepared from 20a (30 mg, 0.067 mmol) in toluene was added dropwise a solution of N-hydroxythiopyridone 22 (11 mg, 0.09 mmol) and DMAP (2 mg) in toluene (0.5 mL) and pyridine (0.3 mL) at room temperature under N2 in the dark. After stirring for 10 min, t-butylmercaptane (0.5 mL) was added and the mixture was irradiated with white light (tungsten lamp, 100 W) at room temperature. After stirring for 10 min, N2 was introduced to the mixture under a slightly reduced pressure to remove residual t-butylmercaptane for 30 min. Usual workup and purification by silica gel preparative TLC [developed with hexane-Et2O (1:)] afforded 21 (18.5 mg, 68%) as an oil, [α]22D +36.8° (c 1.85, CHCl3); 1H NMR (CDCl3) δ2.000-2.150 (2 H, m, H-2ax, H-2eq), 2.010 (6 H, s, acetyl), 2.082 (3 H, s, acetyl), 2.119 (3 H, s, acetyl), 2.137 (3 H, s, acetyl), 3.882 (1 H, dd, J5,4 =1.5, J5,6 =10.0 Hz, H-5), 4.115 (1 H, dd, J7',6 =4.5, J7',7 =12.5 H, H-7'), 4.437 (1 H, dd, J7,6 =2.5, J7,7' =12.5 Hz, H-7), 5.073 (1 H, ddd, J3,4 =3.0, J3,2eq =5.0, J3,2ax =12.5 Hz, H-3), 5.165 (1 H, ddd, J6,7 =2.5, J6,7' =4.5, J6,5 =10.0 Hz, H-6), 5.303 (1 H, dd, J4,5 =1.5, J4,3 =3.0 Hz, H-4), 5.748 (1 H, dd, J1,2eq =3.0, J1,2ax =10.0 Hz, H-1); 13C NMR (CDCl3) δ20.59, 20.59, 20.65, 20.65, 20.84, 30.35, 62.26, 63.84, 67.32, 67.90, 71.62, 91.67, 168.60, 169.60, 169.83, 170.30, 170.54. HRMS (M+Cs+) calcd C17H24O11Cs 537.0373, found 537.0359.

Workup

  1. additiont-butylmercaptane (0.5 mL) was added
  2. stirringAfter stirring for 10 min
  3. customto remove residual t-butylmercaptane for 30 min
  4. customUsual workup and purification by silica gel preparative TLC [developed with hexane-Et2O (1:)]

Sources & evidence

ORD record
ord-8ac4fc830fe4476aa14045fd6d8e84ee
Source dataset
uspto-grants-1999_02
Patent number
US05869316

Reaction notes

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