New Aspects of the Indium Chemistry of Carbonyl-β-lactams

Abstract

Reactions of racemic as well as optically pure carbonyl-β-lactams with stabilized organo-indium reagents were investigated in aqueous media. The regio- and stereochemistry of the processes were generally good, offering a convenient asymmetric entry to densely functionalized hydroxy-β-lactams.

addition reactions - asymmetric synthesis - lactams - indium - organometallic reagents

References

1a Ranu BC. Eur. J. Org. Chem.  2000,  2347 

1b Chauhan KK. Frost CG. J. Chem. Soc., Perkin Trans. 1  2000,  3015 

2 Since the landmark review by Cintas in 1995, the organic chemistry community has witnessed an explosion of interest in the utility of indium reagents in synthesis, see: Cintas P. Synlett  1995,  1087 

3 Li CJ. Chan TH. Tetrahedron  1999,  55:  11149 

See, for example:

4a Niccolai D. Tarsi L. Thomas RJ. Chem. Commun.  1997,  2333 

4b Southgate R. Contemp. Org. Synth.  1994,  1:  417 

4c Southgate R. Branch C. Coulton S. Hunt E. In Recent Progress in the Chemical Synthesis of Antibiotics and Related Microbial Products   Vol. 2:  Lukacs G. Springer; Berlin: 1993.  p.621 

4d The Chemistry of β-Lactams   Page MI. Chapman and Hall; London: 1992A. 

See, for instance:

5a Alcaide B. Almendros P. Synlett  2002,  381 

5b Alcaide B. Almendros P. Chem. Soc. Rev.  2001,  30:  226 

5c Palomo C. Aizpurua JM. Ganboa I. Oiarbide M. Synlett  2001,  1813 

5d Palomo C. Aizpurua JM. Ganboa I. Oiarbide M. Amino Acids  1999,  16:  321 

5e Ojima I. Delaloge F. Chem. Soc. Rev.  1997,  26:  377 

5f Manhas MS. Wagle DR. Chiang J. Bose AK. Heterocycles  1988,  27:  1755 

See, for example:

6a Enders D. Reinhold U. Angew. Chem., Int. Ed. Engl.  1995,  34:  1219 

6b Rich DH. In Peptidase Inhibitors, Comprehensive Medicinal Chemistry   Vol. 2:  Sammes PG. Pergamon Press; Oxford: 1990.  p.391 

6c Huff JR. J. Med. Chem.  1991,  34:  2305 

6d Thaisrivongs S. Pals DT. Kroll LT. Turner SR. Han F.-S. J. Med. Chem.  1987,  30:  976 

7 Cho YS. Lee JE. Pae NA. Choi KI. Koh HY. Tetrahedron Lett.  1999,  40:  1725 

8 Jayaraman M. Manhas MS. Bose AK. Tetrahedron Lett.  1997,  38:  709 

9 Paquette LA. Rothhaar RR. Isaac M. Rogers LM. Rogers RD. J. Org. Chem.  1998,  63:  5463 

For recent selected reviews on organic reaction in aq media, see:

10a Lindström UM. Chem. Rev.  2002,  102:  2751 

10b Manabe K. Kobayashi S. Chem.-Eur. J.  2002,  8:  4095 

10c Paquette LA. In Green Chemistry: Frontiers in Benign Chemical Synthesis and Processing   Anastas PT. Williamson TC. Oxford University Press; New York: 1998. 

10d Lubineau A. Augé J. Top. Curr. Chem.  1999,  206:  1 

Similar results were obtained using zinc instead of indium, see:

11a Alcaide B. Almendros P. Aragoncillo C. Rodríguez-Acebes R. J. Org. Chem.  2001,  66:  5208 

11b Alcaide B. Almendros P. Aragoncillo C. Org. Lett.  2000,  2:  1411 

12

The zinc-mediated reaction gave rise to the corresponding homopropargyl alcohol as a single isomer, see reference. [11]

13 The zinc-mediated reaction afforded the syn-adducts with complete regioselectivity and good diastereoselectivity, see: Alcaide B. Almendros P. Aragoncillo C. Chem.-Eur. J.  2002,  8:  1719 

14 When the above coupling was promoted by zinc, the yield fell considerably, see: Alcaide B. Almendros P. Rodríguez-Acebes R. J. Org. Chem.  2002,  67:  1925 

15 Chan has postulated that an allylindium(I) intermediate is formed in indium-mediated organometallic reactions in aqueous media, see: Chan TH. Yang Y. J. Am. Chem. Soc.  1999,  121:  3228