New synthetic technology for the synthesis of hindered α-diazoketones via acyl mesylates

Organic Letters

Volumn 1, Issue 6, 1999, Pages 883-886

  Nicolaou, K C ^a   Baran, Phil S ^a   Zhong, Yong Li ^a   Choi, Ha Soon ^a   Fong, Kin Chiu ^a   He, Yun ^a   Yoon, Won Hyung ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

KETONE; MESYLIC ACID DERIVATIVE;

ARTICLE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

KETONES; MAGNETIC RESONANCE SPECTROSCOPY; MESYLATES;

EID: 0033598268     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol990790l     Document Type: Article

References (18)

1. Askani, R.; Taber, D. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 6, p 126.
2. Reference 1, p 126. See also: Atkinson, R. S. In Comprehensive Organic Synthesis; Barton, D. H. R., Ollis, W. D., Eds.; Pergamon Press: Oxford, 1979; Vol. 2, p 246.
3. Part 1: Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Choi, H.-S.; Yoon, W. H.; He, Y.; Fong, K. C. Angew. Chem. Int. Ed. 1999, 38, 1669. Part 2: Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Fong, K. C.; He, Y.; Yoon, W. H.; Choi, H.-S. Angew. Chem. Int. Ed. 1999, 38, 1676. For an additional rationale for the employment of acyl mesylates to construct hindered diazoketones, see Scheme 9 of Part 1.
4. Part 1: Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Choi, H.-S.; Yoon, W. H.; He, Y.; Fong, K. C. Angew. Chem. Int. Ed. 1999, 38, 1669. Part 2: Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Fong, K. C.; He, Y.; Yoon, W. H.; Choi, H.-S. Angew. Chem. Int. Ed. 1999, 38, 1676. For an additional rationale for the employment of acyl mesylates to construct hindered diazoketones, see Scheme 9 of Part 1.
5. (a) Dunn, A. D.; Mills, M. J.; Henry, W. Org. Prep. Proced. Int. 1982, 14, 396.
6. (b) Chandrasekaran, S.; Turner, J. V. Synth. Commun. 1982, 12, 727.
7. (c) Jászay, Z. M.; Petneházy, I.; Töke, L. Synthesis 1989, 745. For work on acyl fluorosulphonates, see: Olah, G. A.; Narang, S. C.; Garcia-Luna, A. Synthesis 1981, 790.
8. (c) Jászay, Z. M.; Petneházy, I.; Töke, L. Synthesis 1989, 745. For work on acyl fluorosulphonates, see: Olah, G. A.; Narang, S. C.; Garcia-Luna, A. Synthesis 1981, 790.
9. Arndt, F.; Eistert, B. Ber. Dtsch. Chem. Ges. 1935, 68B, 200. We had identified the Arndt-Eistert reaction as the most prudent method to complete the quartenary center after a series of model studies which will be delineated in a full account of ref 3.
10. For leading references, see: Marson, C. M.; Giles, P. R. Synthesis Using Vilsmeir Reagents; CRC Press: Boca Raton, FL, 1994.
11. For a related synthesis of compound 17, see: Nicolaou, K. C.; Mitchell, H. J.; Jain, N. F.; Winssinger, N.; Hughes, R.; Bando, T. Angew. Chem. Int. Ed. 1999, 38, 240; Nicolaou, K. C.; Mitchell, H. J.; Jain, N. F.; Winssinger, N.; Hughes, R.; Bando, T., Koumbis, A, Natarajan, S. Chem. Eur. J. 1999, in press. Special thanks to N. Winssinger for a generous sample of 17.
12. For a related synthesis of compound 17, see: Nicolaou, K. C.; Mitchell, H. J.; Jain, N. F.; Winssinger, N.; Hughes, R.; Bando, T. Angew. Chem. Int. Ed. 1999, 38, 240; Nicolaou, K. C.; Mitchell, H. J.; Jain, N. F.; Winssinger, N.; Hughes, R.; Bando, T., Koumbis, A, Natarajan, S. Chem. Eur. J. 1999, in press. Special thanks to N. Winssinger for a generous sample of 17.
13. In this instance, 1,2-dichloroethane proved to be a superior solvent to acetonitrile. The dehydration of primary amides to the corresponding nitriles with methanesulphonyl chloride is known: see ref 4a. Acid 17 is completely unreactive with conventional esterification methods due to the extreme steric shielding present in its vicinity.
14. 2.
15. The use of methanesulfonyl chloride in the synthesis of symmetrical anhydrides is known: Nangia, A.; Chandrasekaran, S. J. Chem. Res., Synop. 1984, 100.
16. For the synthesis of 25, see: Nicolaou, K. C.; Pfefferkorn, J. A.; Kim, S.; Wei, H.-X. J. Am. Chem. Soc. 1999, 121, 4724. J. Pfefferkorn is gratefully acknowledged for providing a generous sample of 25.
17. Brewster, J. H.; Ciotti, C. J., Jr. J. Am. Chem. Soc. 1955, 77, 6214.
18. 2, hexanes:EtOAc 5:1) furnished an inseparable mixture of diazoketone 10 and methyl ester 11 (6:1) in 86% yield.