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Synlett 2014; 25(1): 133-137
DOI: 10.1055/s-0033-1340159
DOI: 10.1055/s-0033-1340159
letter
Synthesis of Heterocycles Based on Rhodium-Catalyzed C–H Amination
Further Information
Publication History
Received: 26 August 2013
Accepted after revision: 25 September 2013
Publication Date:
06 November 2013 (online)
Abstract
A new stereoselective approach to substituted pyrrolidines and piperidines is described that involves Du Bois’ C–H amination reaction, Boc-activation of a cyclic sulfamate group, and base-promoted intramolecular cyclization. This methodology can be utilized for the synthesis of tetrahydrofuran and tetrahydrothiophene derivatives.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
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- 8 Preparation of 8a from 4 via 5, 6a, and 7a; Sulfamate 5: Formic acid (0.69 mL, 15 mmol) was added to neat chlorosulfonyl isocyanate (1.3 mL, 15 mmol) at 0 °C and the mixture was stirred for 5 min. MeCN (10 mL) was added and the mixture was stirred at r.t. for 8 h to generate sulfamoyl chloride (1.5 M in MeCN). To an ice-cooled solution of 4 (1.40 g, 4.28 mmol) in DMA (10 mL) and MeCN (10 mL) was added sulfamoyl chloride (1.5 M in MeCN, 5.7 mL, 8.56 mmol). The mixture was stirred at r.t. for 1 h and saturated NaHCO3 (5 mL) was added at 0 °C. The mixture was extracted with EtOAc, washed with brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (SiO2 30 g; hexane–EtOAc, 4:1 to 1:1) gave 5 (1.70 g, 97%) as a colorless amorphous solid. Cyclic Sulfamate 6a: To a solution of 5 (411 mg, 1.08 mmol) in CH2Cl2 (10 mL) at r.t. were added MgO (100 mg, 2.50 mmol), PhI(OAc)2 (BAIB; 354 mg, 1.12 mmol), and Rh2(OAc)4 (9 mg, 0.02 mmol). After stirring at r.t. for 2 h, the mixture was filtered through cotton and concentrated in vacuo. Purification of the residue by column chromatography (SiO2 30 g; hexane–EtOAc, 3.5:1 to 1.5:1) gave 6a (371 mg, 84%) as a colorless amorphous solid. N-Boc Sulfamate 7a: To a stirred solution of 6a (1.10 g, 0.75 mol) in CH2Cl2 (20 mL) at r.t. were added Et3N (0.59 mL, 4.08 mmol), Boc2O (712 mg, 0.98 mmol), and DMAP (33 mg, 0.27 mmol). After stirring at r.t. for 5 h, the mixture was extracted with EtOAc, washed with brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (SiO2 15 g; hexane–EtOAc, 4:1) gave 7a (1.10 g, 80%) as a colorless amorphous solid. Pyrrolidine 8a: To an ice-cooled solution of 7a (100 mg, 0.20 mmol) in DMF (2 mL) was added NaH (60% in mineral oil, 16 mg, 0.40 mmol). The mixture was stirred at 0 °C for 5 min, then H2O (36 μL, 2.0 mmol) was added and the mixture was stirred at r.t. for 5 min. The mixture was neutralized with 1 M HCl, extracted with EtOAc, washed with sat. NaHCO3 and brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (SiO2 5 g; hexane–EtOAc, 5:1) gave 8a (83 mg, 99%) as a colorless solid.
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- 11 Representative One-Pot Preparation (Method B): Et3N (0.05 mL, 0.38 mmol), DMAP (3 mg, 0.025 mmol), and Boc2O (72 mg, 0.33 mmol) were added to a solution of 6a (100 mg, 0.25 mol) in DMF (2 mL) at r.t. The mixture was stirred at r.t. for 5 h, then NaH (60% in mineral oil, 30 mg, 0.75 mmol) was added at 0 °C. The mixture was stirred at 0 °C for 5 min, then H2O (45 μL, 2.5 mmol) was added, and the mixture was stirred at r.t. for 5 min. The mixture was neutralized with 1 M HCl, extracted with EtOAc, washed with saturated NaHCO3 and brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (SiO2 5 g; hexane–EtOAc, 5:1) gave 8a (85 mg, 81%) as a colorless solid.
- 12 The crystallographic data (CCDC 943270) can be obtained free of charge from the Cambridge Crystallographic Data centre via www.ccdc.cam.ac.uk/data_request/cif.
- 13 The crystallographic data (CCDC 943271) can be obtained free of charge from the Cambridge Crystallographic Data centre via www.ccdc.cam.ac.uk/data_request/cif.
For recent reviews, see:
For methodologies for heterocycle synthesis recently developed by our group, see:
For reviews, see:
For heterocycle syntheses utilizing Rh-catalyzed C–H amination, see:
For related water-promoted displacement reactions, see: