Nucleophilic Addition of α-Metallated Carbamates to Planar Chiral Cationic η³-Allylmolybdenum Complexes: A Stereochemical Study

Abstract

Chiral α-(O-carbamoyl)alkyl- and α-(N-carbamoyl)al­kylcopper(I) reagents derived from (-)-sparteine-mediated asymmetric lithiation of hindered carbamates react with cationic η³-allylmolybdenum complexes with retention of configuration.

Key words

(-)-sparteine - nucleophilic addition - η³-allylmolybdenum complexes - asymmetric deprotonation - carbamates - α-(O-carbamoyl)alkylcopper(I) - α-(N-carbamoyl)alkylcopper(I)

References

• 1 Kocienski PJ. Brown RCD. Pommier A. Procter M. Schmidt B. J. Chem. Soc., Perkin Trans. 1  1998,  9 
• 2 Cohen T. Bhupathy M. Acc. Chem. Res.  1989,  22:  152 
• 3 Freeman PK. Hutchinson LL. J. Org. Chem.  1980,  45:  1924 
• 4 Giese B. Dupuis J. Tetrahedron Lett.  1984,  25:  1349 
• 5 Rychnovsky SD. Powers JP. Lepage TJ. J. Am. Chem. Soc.  1992,  114:  8375 
• The transmetallation of chiral α-alkoxyalkyllithiums to the corresponding cuprates and their conjugate addition to enones occur with retention of configuration:
• 6a Hutchinson DK. Fuchs PL. J. Am. Chem. Soc.  1987,  109:  4930 
• 6b See also: Calter MA. Bi FC. Org. Lett.  2000,  2:  1529 
• 7 For a review see: Dieter RK. Heteroatom Cuprates and α-Heteroatomalkylcuprates in Organic Synthesis, In Modern Organocopper Chemistry   Krause N. Wiley; New York: 2002.  Chap. 3. p.79 
• 8 Sinz CJ. Rychnovsky SD. Top. Curr. Chem.  2001,  216:  51 
• 9 Christopher JA. Kocienski P. Procter M. Synlett  1998,  425 
• 10 Hoppe D. Hense T. Angew. Chem., Int. Ed. Engl.  1997,  36:  2283 
• 11 Hoppe D. Marr F. Brüggemann M. Enantioselective Synthesis by Lithiation Adjacent to Oxygen and Electrophile Incorporation, In Organolithiums in Enantioselective Synthesis   Hodgson DM. Springer; Berlin: 2003.  p.61-137  
• 12 Haller J. Hense T. Hoppe D. Liebigs Ann. Chem.  1994,  489 
• 13 Tomooka K. Shimizu H. Nakai T. J. Organomet. Chem.  2001,  624:  364 
• 14 Matsumoto T. Hosoda Y. Mori K. Fukui K. Bull. Chem. Soc. Jpn.  1972,  45:  3156 
• 15 Helmke H. Hoppe D. Synlett  1995,  978 
• 16 Kocienski PJ. Yeates C. Street SDA. Campbell SF. J. Chem. Soc., Perkin Trans. 1  1987,  2183 
• 17 Ishikawa T. Ikeda S. Ibe M. Saito S. Tetrahedron  1998,  54:  5869 
• 18 Beak P. Johnson TA. Kim DD. Lim SH. Enantioselective Synthesis by Lithiation Adjacent to Nitrogen and Electrophile Incorporation, In Organolithiums in Enantioselective Synthesis   Hodgson DM. Springer; Berlin: 2003.  p.140-176  
• 19 Bertini Gross KM. Jun YM. Beak P. J. Org. Chem.  1997,  62:  7679 
• 20 Dieter and co-workers recently reported the enantioselective alkylation of α-(N-carbamoyl)alkylcuprates with allylic phosphates: Dieter RK. Gore VK. Chen N. Org. Lett.  2004,  6:  763 
• 21 Faller JW. Linebarrier D. Organometallics  1988,  7:  1670 
• 22 Gao Y. Hanson RM. Klunder JM. Ko SY. Masamune S. Sharpless KB. J. Am. Chem. Soc.  1987,  109:  5765 
• 23 Anderson EM. Larsson KM. Kirk O. Biocatal. Biotransform.  1998,  16:  181 
• 25 Cooksey J. Gunn A. Kocienski PJ. Kuhl A. Uppal S. Christopher JA. Bell R. Org. Biomol. Chem.  2004,  2:  1719 
• 26 Papillon and Taylor recently reported the alkylation and conjugate addition of chiral α-(O-carbamoyl)alkylzinc cuprates: Papillon JPN. Taylor RJK. Org. Lett.  2002,  4:  119 
• 27 Matteson DS. Tripathy PB. Sarkar A. Sadhu KM. J. Am. Chem. Soc.  1989,  111:  4399 
• 28 Theis AB. Townsend CA. Synth. Commun.  1981,  11:  157 
• 29 Lipton MF. Sorensen CM. Sadler AC. Shapiro RH. J. Organomet. Chem.  1980,  186:  155 
• 31 Hintze F. Hoppe D. Synthesis  1992,  1216 
• 32 Iwao M. Kuraishi T. Crowley J. Martin SF. Org. Synth.  1995,  73:  85 
• 33 Meyers AI. Milot G. J. Org. Chem.  1993,  58:  6538 
• 34 Anderson WK. Lai G. Synthesis  1995,  1287 
• 35 Iwao M. Kuraishi T. Heterocycles  1992,  34:  1031 
• 36 Fleming I. Higgins D. Lawrence NJ. Thomas AP. J. Chem. Soc., Perkin Trans. 1  1992,  3331 

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Attempts to accomplish a similar enzymatic resolution of (±)-33 failed.

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The supplementary crystallographic data for this structure (CCDC 247732) can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing [e-mail], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK.