A Convenient Allylic Functionalization of Bis(prop-2-enyl)methanol by Direct Trimetalation

Abstract

A practical synthesis of functionalized symmetrical dialkenylcarbinols­ has been developed. Key feature is a direct trilithiation of readily available bis(prop-2-enyl)methanol followed by trapping of the trianion with various electrophiles. This simple protocol allows rapid derivatization and preparation of compounds inaccessible by currently existing methods.

alkenes - alcohols - lithiation - metalations - organometallic reagent

References

1a Poss CS. Schreiber SL. Acc. Chem. Res.  1994,  27:  9 

1b Willis MC. J. Chem. Soc., Perkin Trans. 1  2001,  1765 

2 Schreiber TS. Smith DB. Schreiber SL. J. Am. Chem. Soc.  1987,  109:  1525 

3 Tamao K. Tohma T. Inui N. Nakayama O. Ito Y. Tetrahedron Lett.  1990,  31:  7333 

4 Mikami K. Narisawa M. Shimizu M. Terada M. J. Am. Chem. Soc.  1992,  114:  6566 

5 Martin SF. Spaller MR. Liras S. Hartmann B. J. Am. Chem. Soc.  1994,  116:  4493 

6 Dolman S. Hultzsch KC. Pezet F. Teng X. Hoveyda AH. Schrock RR. J. Am. Chem. Soc.  2004,  126:  10945 ; and references cited therein

7a Breit B. Breuninger D. J. Am. Chem. Soc.  2004,  126:  10244 

7b Breit B. Breuninger D. Eur. J. Org. Chem.  2005,  3916 

8 Depezay JC. Ficini J. Bull. Soc. Chim. Fr.  1966,  3878 

9 Boccara N. Maitte P. Bull. Soc. Chim. Fr.  1972,  1448 

10 Carillo G. Contento M. Sandri S. Tetrahedron Lett.  1974,  25:  2215 

11a Trost BM. Chan DMT. Nanninga TN. Org. Synth. Coll. Vol. 7   Wiley; New York: 1990.  p.266 

11b Trost BM. King SA. J. Am. Chem. Soc.  1990,  112:  408 

12 For a similar observation, see: Trost BM. Nanninga TN. J. Am. Chem. Soc.  1985,  107:  1293 

13

A similar protocol as in reference 11a was used. See experimental section.

14 Gouverneur V. Thibaudeau S. Org. Lett.  2003,  5:  4891 

15 Love BE. Jones EG. J. Org. Chem.  1999,  64:  3755 

16 Murphy JA. Mahesh M. McPheators G. Anand RV. McGuire TM. Carlinga R. Kennedy AR. Org. Lett.  2007,  9:  3233