Indium-Mediated Allenylation and Propargylation of Allenic Alcohols with Prop-2-ynyl Bromides

Abstract

Indium was found to mediate the reaction between aldehydes and 1-bromo-2-butyne to give E-1-substituted-2,5-dimethyl-heptatrien-1-ol compounds in moderate to good yields. The reaction was extended to the regio- and stereoselective allenylation and propargylation of allenic alcohols with different prop-2-ynyl bromides in the presence of indium and indium tribromide under ultrasonic irradiation.

indium - allenylation - propargylation - allenic alcohols - prop-2-ynyl bromides

References

For review, see:

1a Cintas P. Synlett  1995,  1087 

1b Li CJ. Chan TH. Organic Reactions in Aqueous Media   John Wiley & Sons; New York: 1997. 

1c Paquette LA. In Green Chemistry: Frontiers in Benign Chemical Synthesis and Processing   Anastas P. Williamson T. Oxford University Press; New York: 1998. 

1d Li CJ. Chan TH. Tetrahedron  1999,  55:  11149 

2a Araki S. Ito H. Butsugan Y. J. Org. Chem.  1988,  53:  1831 

2b Li CJ. Chan TH. Tetrahedron Lett.  1991,  32:  7017 

2c Paquette LA. Mitzel TM. J. Org. Chem.  1996,  61:  8799 

2d Paquette LA. Mitzel TM. J. Org. Chem.  1998,  63:  5604 

2e Chan TH. Yang Y. J. Am. Chem. Soc.  1999,  121:  3228 

2f Hirashita T. Yamamura H. Kawai M. Araki S. Chem. Commun.  2001,  387 

3a Isaac MB. Chan T.-H. J. Chem. Soc., Chem. Commun.  1995,  1003 

3b Yi X.-H. Meng Y. Hua X.-G. Li C.-J. J. Org. Chem.  1998,  63:  7472 

4a Araki S. Imai A. Shimizu K. Butsugan Y. Tetrahedron Lett.  1992,  33:  2581 

4b Araki S. Imai A. Shimizu K. Yamada M. Mori A. Butsugan Y. J. Org. Chem.  1995,  60:  1841 

5 Araki S. Usui H. Kato M. Butsugan Y. J. Am. Chem. Soc.  1996,  118:  4690 ; and references cited therein

6 Fujiwara N. Yamamoto Y. J. Org. Chem.  1997,  62:  2318 

For review, see:

7a Knochel P. Comprehensive Organomentallic Chemistry II   Vol. 11:  Able EW. Stone FGA. Wilkinson G. Pergamon Press; Oxford: 1995.  p.159 

7b Knochel P. Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Flemming I. Pergamon Press; Oxford: 1991.  p.865 

7c Yamamoto Y. Asao N. Chem. Rev.  1993,  93:  2207 

7d Oppolzer W. Angew. Chem., Int. Ed. Engl.  1989,  28:  38 

For review, see:

8a Yamamoto H. Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Flemming I. Pergamon Press; Oxford: 1991.  p.81 

8b Tsuji J. Mandai T. Angew. Chem., Int. Ed. Engl.  1995,  34:  2589 

For examples of using indium halides as Lewis acid, see reference^1d and:

9a Yadav JS. Reddy BVS. Synthesis  2002,  511 

9b Ghosh R. Indian. J. Chem., Sect. B   2001,  40:  550 

9 For evidence regarding the formation of indium(III) intermediates from the reaction of propargyl bromides with indium in THF, see: Miao W. Lu W. Chan TH. J. Am. Chem. Soc.  2003,  125: 2412

11a Zhang L. Huang Y. Huang Z. Tetrahedron Lett.  1991,  32:  6579 

11b Masuyama Y. Watabe A. Ito A. Kurusu Y. Chem. Commun.  2000,  2009 

12 Zhou J.-Y. Sun G.-F. Zhang M.-F. Jia Y. Wu S.-H. Chin. J. Chem.  1997,  15:  361