Bis(chloromethyl) Sulfone and Sulfoxide as Precursors of the Corresponding α,α′-Dianionic Synthons by a Chlorine-Lithium Exchange

Abstract

The DTBB-catalyzed lithiation of bis(chloromethyl) sulfone (1) and sulfoxide (3) in the presence of different carbonyl compounds [t-BuCHO, c-C₆H₁₁CHO, PhCHO, Me₂CO, Et₂CO, n-Pr₂CO, (CH₂)₄CO, (CH₂)₅CO, (c-C₃H₅)₂CO, PhCOMe, norbonan-2-one] in THF at -90 ºC, followed by hydrolysis with water at the same temperature led to the formation of the corresponding dihydroxy sulfones (2) or sulfoxides (4). Representative compounds of both series have been analyzed by X-ray crystallography.

dimethyl sulfone dianion - dimethyl sulfoxide dianion - DTBB-catalyzed lithiation - chloro-lithium exchange

References

1

Carried out X-ray analyses. New address: Servicios Técnicos de Investigación, Planta Cero, Facultad de Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain.

For general monographs see:

2a Wakefield BJ. Organolithium Methods   Academic Press; London: 1988. 

2b Lithium Chemistry: A Theoretical and Experimental Overview   Sapse A.-M. Schleyer PV. John Wiley & Sons; New York: 1995. 

2c Gray M. Tinkel M. Sniekus V. In Comprehensive Organometallic Chemistry II   Vol. 11:  Abel EW. Stone FGA. Wilkinson G. McKillop A. Pergamon; Oxford: 1995.  p.1-92  

2d Clayden J. Organolithiums: Selectivity for Synthesis   Pergamon; Oxford: 2002. 

3 Simpkins NS. Sulphones in Organic Synthesis   Pergamon Press; Oxford: 1993. 

4 The Chemistry of Sulphones and Sulphoxides   Patai S. Rappoport Z. Stirling C. John Wiley & Sons; Chichester: 1988. 

5 Kaiser EM. Beard RD. Hauser CR. J. Organomet. Chem.  1973,  59:  53 

For α,α′-dianions of other substituted or stabilized sulfones see for instance:

6a Paquette LA. Meisinger RH. Gleiter R. J. Am. Chem. Soc.  1973,  95:  5414 

6b Gossert JS. Buter J. Asveld EWH. Kellogg RM. Tetrahedron Lett.  1974,  2805 

For reviews see:

7a Yus M. Chem. Soc. Rev.  1996,  25:  155 

7b Ramón DJ. Yus M. Eur. J. Org. Chem.  2000,  225 

7c Yus M. Synlett  2001,  1197 

7d Yus M. Ramón DJ. Lat. J. Chem.  2002,  79 

7e Ramón DJ. Yus M. Rev. Cubana Quim.  2002,  14:  75 

7f Yus M. In The Chemistry of Organolithium Compounds   Vol. 1, Part 2:  Rappoport Z. Marek I. J. Wiley & Sons; Chichester: 2004.  Chap. 11.

For mechanistic studies see:

8a Yus M. Herrera RP. Guijarro A. Tetrahedron Lett.  2001,  42:  3455 

8b Yus M. Herrera RP. Guijarro A. Chem.-Eur. J.  2002,  8:  2574 

8c Yus M. Herrera RP. Guijarro A. Tetrahedron Lett.  2003,  44:  1309 

8d Yus M. Herrera RP. Guijarro A. Tetrahedron Lett.  2003,  44:  1313 

8e Yus M. Herrera RP. Guijarro A. Tetrahedron Lett.  2003,  44:  5025 

For a polymer supported arene-catalyzed version of this reaction see:

8f Gómez C. Ruiz S. Yus M. Tetrahedron Lett.  1998,  39:  1397 

8g Gómez C. Ruiz S. Yus M. Tetrahedron  1999,  55:  7017 

8h Yus M. Candela P. Gómez C. Tetrahedron  2002,  58:  6207 

8i Arnauld T. Barret AGM. Hopkins BT. Tetrahedron Lett.  2002,  43:  1081 

8j Alonso F. Gómez C. Candela P. Yus M. Adv. Synth. Catal.  2003,  345:  275 

8k Candela P. Gómez C. Yus M. Russ. J. Org. Chem. (Engl. Transl.)  2004,  40:  795 

9 For a review on the Barbier reaction see: Alonso F. Yus M. Recent Res. Dev. Org. Chem.  1997,  1:  397 

10

The single chlorine-lithium exchange (for instance a stoichiometric amount of Li) failed, giving a complex mixture of reaction products.

11

Under Barbier conditions not many electrophiles are compatible with the strongly reducing reaction mixture carbonyl compounds being appropriate for that purpose.

For reviews see:

12a Nájera C. Yus M. Trends Org. Chem.  1991,  2:  155 

12b Nájera C. Yus M. Org. Prep. Proced. Int.  1995,  27:  383 

12c Nájera C. Yus M. Recent Res. Dev. Org. Chem.  1997,  1:  67 

12d Nájera C. Yus M. Curr. Org. Chem.  2003,  7:  867 

12e Nájera C. Sansano JM. Yus M. Tetrahedron  2003,  59:  9255 

12f Chinchilla R. Nájera C. Yus M. Chem. Rev.  2004,  104:  2667 

12g See also Functionalised Organolithium Compounds, In Tetrahedron Symposium in Print; Nájera, C., Yus, M., Eds.; Tetrahedron  2005,  61 (13):  3125-3450  

13 Clayden J. Samreen SA. New J. Chem.  2002,  26:  191 ; and references cited therein

14 See for instance: Eliel EL. Wilen SH. Stereochemistry of Organic Compounds   John Wiley & Sons; New York: 1994.  p.736 

15 Truce WE. Birum GH. McBee ET. J. Am. Chem. Soc.  1952,  74:  3594 

16 Venier CG. Squires TG. Chen YY. Smith BF. J. Org. Chem.  1982,  47:  3773 

For reviews see:

17a Yus M. Foubelo F. Rev. Heteroat. Chem.  1997,  17:  73 

17b Yus M. Foubelo F. Targets in Heterocyclic Systems   Vol. 6:  Attanasi OA. Spinelli D. Italian Society of Chemistry; Rome: 2002.  p.136 

17c Yus M. Pure Appl. Chem.  2003,  75:  1453 

18 Almena J. Ph.D. Dissertation   University of Alicante; Spain: 1996. see also reference 17b

19 Yus M. Ortiz R. Huerta FF. Tetrahedron  2003,  59:  8525 

20 Yus M. Martínez P. Guijarro D. Tetrahedron  2001,  57:  10119