Synlett 2018; 29(05): 678-682
DOI: 10.1055/s-0036-1589156
letter
© Georg Thieme Verlag Stuttgart · New York

Sulfonyl as a Traceless Activation Group for Enantioselective Mannich Reaction Catalyzed by Thiourea to Access Chiral β-Aminophosphonates

Yungui Peng*
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. of China   Email: pengyungui@hotmail.com   Email: pyg@swu.edu.cn
,
Yanqiang Ning
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. of China   Email: pengyungui@hotmail.com   Email: pyg@swu.edu.cn
,
Songlin Tan
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. of China   Email: pengyungui@hotmail.com   Email: pyg@swu.edu.cn
,
Dezhong Li
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. of China   Email: pengyungui@hotmail.com   Email: pyg@swu.edu.cn
,
Na Liao
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. of China   Email: pengyungui@hotmail.com   Email: pyg@swu.edu.cn
› Author Affiliations
We are grateful for financial support from the National Science Foundation of China (21172180).
Further Information

Publication History

Received: 15 October 2017

Accepted after revision: 27 November 2017

Publication Date:
19 January 2018 (eFirst)

◊ These authors contributed equally

Abstract

An efficient enantioselective Mannich reaction of N-protected α-sulfones with β-benzenesulfonyl phosphonates was developed by using a chiral cinchona alkaloid-derived thiourea as a catalyst. This method was used to obtain a series of chiral α-sulfonyl-β-aminophosphonates in yields of up to 96% with 89:11 dr and 88% ee. These compounds were further transformed into β-aminophosphonates or chiral azetidines with various functional groups by a Horner–Wadsworth–Emmons/aza-Michael addition reaction sequence.

Supporting Information

 
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  • 11 Mannich Products 4 and Aminophosphonates 5; General Procedure The N-protected α-amido sulfone 1 (0.12 mmol, 1.2 equiv), 3e (10 mol%), and LiOH·H2O (0.14 mmol, 1.4 equiv) were dissolved in toluene (1.0 mL) at –20 °C, and the mixture was stirred for 5 min. β-Benzenesulfonyl phosphate 2 (0.1 mmol, 1.0 equiv) was added at –20 °C, and the mixture was stirred for 72 h. The reaction was quenched with sat. aq NH4Cl, and the aqueous layer was extracted with EtOAc (3 × 30 mL). The organic phases were combined, dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product 4 was purified by chromatography [silica gel, EtOAc–PE]. 1,2-Dibromoethane (50 µL) was added to a mixture of product 4 and Mg turnings (30 equiv) in anhyd MeOH (0.1 mmol/mL) at 0 °C, and the mixture was stirred at r.t. for 11 h. The reaction was then quenched with sat. aq NH4Cl and the mixture was filtered. The aqueous layer was extracted with EtOAc. The organic phases were combined, dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product was then purified by chromatography [silica gel, EtOAc–PE]. Diethyl ((2S)-2-Phenyl-2-{[(1,1,2-trimethylpropoxy)carbonyl]-­amino}ethyl)phosphonate (5ba) Prepared from 4ba (32 mg, 0.060 mmol), Mg turnings (44 mg, 1.80 mmol), and 1,2-dibromoethane (50 µL), as described above, as a colorless oil; yield: 19 mg (81%), [α]D 25 + 13.7 (c = 0.38, CH2Cl2). HPLC: Chiralpak ID column [hexane–i-PrOH (80:20), flow rate: 0.5 mL/min, λ = 254 nm]: t minor = 25.6 min, t major = 29.8 min. 1H NMR (600 MHz, CDCl3): δ = 7.31 (s, 4 H), 7.24 (s, 1 H), 5.81 (s, 1 H), 5.03 (s, 1 H), 4.03 (s, 2 H), 3.85 (d, J = 54.0 Hz, 2 H), 2.42–2.13 (m, 3 H), 1.35 (s, 6 H), 1.28 (t, J = 6.0 Hz, 3 H), 1.14 (s, 3 H), 0.93–0.73 (m, 6 H). 13C NMR (151 MHz, CDCl3): δ = 154.9, 142.3, 128.5, 127.3, 126.0, 84.8, 61.8 (d, J = 7.5 Hz), 61.6 (d, J = 6.0 Hz), 50.3, 36.2, 33.2 (d, J = 140.4 Hz), 23.1, 23.0, 17.3, 16.3 (d, J = 6.0 Hz), 16.2 (d, J = 6.0 Hz). HRMS (ESI): m/z [M + Na]+ Calcd for C19H32NNaO5P: 408.1916; found: 408.1918.