Direct transformation of allylic and benzylic thiols, thioethers, and disulfides into organolithium compounds

Synthetic Communications

Volumn 33, Issue 13, 2003, Pages 2365-2376

  Yus, Miguel ^a   Martínez, Pedro ^a   Guijarro, David ^a  

^a UNIVERSITY OF ALICANTE   (Spain)

Author keywords

Carbon sulfur bond cleavage; Disulfide; Lithium; Organolithium; Sulfide; Thiol

Indexed keywords

DISULFIDE; ORGANOLITHIUM COMPOUND; SULFIDE; THIOL DERIVATIVE;

ARTICLE; CHEMICAL BOND; LITHIATION; SYNTHESIS;

EID: 0038691529     PISSN: 00397911     EISSN: None     Source Type: Journal    
DOI: 10.1081/SCC-120021518     Document Type: Article

References (62)

1. Barrett, G.C. Thiols. In Comprehensive Organic Chemistry; Barton, D., Ollis, W.D., Eds.; Pergamon Press: Oxford, England, 1979; Vol. 3, Chapter 11.1.
2. (a) Patai, S. The Chemistry of the Thiol Group; Wiley: New York, 1974;
3. (b) Ohno, A.; Oae, S. In Organic Chemistry of Sulphur; Oae, S., Ed.; Plenum: New York, 1976.
4. Sulphides. Ref.[1], Chapter 11.3.
5. (a) Caubère, P.; Coutrot, P. Reduction of sulfur-carbon bonds and of other heteroatoms bonded to tetrahedral carbon. In Comprehensive Organic Synthesis; Trost, B.M., Fleming, I., Eds.; Pergamon: Oxford, England, 1991; Vol. 8, 835;
6. (b) Larock, R.C. Sulfur compounds. In Comprehensive Organic Transformations; John Wiley & Sons: New York, 1999; p. 53.
7. For some examples of this transformation, see: (a) Oae, S.; Togo, H. Facile conversion of aliphatic sulfonic acids, sulfinic acids, thiols, sulfonates, thiolsulfonates, and disulfides to the corresponding alkyl iodides by triphenylphosphine/iodine. Synthesis 1981, 371; (b) Still, I.W.J.; Kutney, G.W.; McLean, D.J. Convenient method for the conversion of thiols and disulfides to the corresponding chlorides. Org. Chem. 1982, 47, 560; (c) Krafft, G.A.; Siddall, T.L. Stereospecific displacement of sulfur from chiral centers. Activation via thiaphosphonium salts. Tetrahedron Lett. 1985, 26, 4867.
8. For some examples of this transformation, see: (a) Oae, S.; Togo, H. Facile conversion of aliphatic sulfonic acids, sulfinic acids, thiols, sulfonates, thiolsulfonates, and disulfides to the corresponding alkyl iodides by triphenylphosphine/iodine. Synthesis 1981, 371; (b) Still, I.W.J.; Kutney, G.W.; McLean, D.J. Convenient method for the conversion of thiols and disulfides to the corresponding chlorides. Org. Chem. 1982, 47, 560; (c) Krafft, G.A.; Siddall, T.L. Stereospecific displacement of sulfur from chiral centers. Activation via thiaphosphonium salts. Tetrahedron Lett. 1985, 26, 4867.
9. For some examples of this transformation, see: (a) Oae, S.; Togo, H. Facile conversion of aliphatic sulfonic acids, sulfinic acids, thiols, sulfonates, thiolsulfonates, and disulfides to the corresponding alkyl iodides by triphenylphosphine/iodine. Synthesis 1981, 371; (b) Still, I.W.J.; Kutney, G.W.; McLean, D.J. Convenient method for the conversion of thiols and disulfides to the corresponding chlorides. Org. Chem. 1982, 47, 560; (c) Krafft, G.A.; Siddall, T.L. Stereospecific displacement of sulfur from chiral centers. Activation via thiaphosphonium salts. Tetrahedron Lett. 1985, 26, 4867.
10. (a) Pastor, S.D.; Hessell, E.T. Substitution of unactivated aryl halides by thiolate anions in polyglymes. J. Org. Chem. 1985, 50, 4812;
11. (b) Barañano, D.; Hartwig, J.F. Carbon-heteroatom bond-forming reductive elimination. Mechanism, importance of trapping reagents, and unusual electronic effects during formation of aryl sulfides. J. Am. Chem. Soc. 1995, 117, 2937;
12. (c) Zheng, N.; McWilliams, J.C.; Fleitz, F.J.; Armstrong, III, J.D.; Volante, R.P. Palladium-catalyzed synthesis of aryl sulfides from aryl triflates. J. Org. Chem. 1998, 63, 9606.
13. (a) Wakefield, B.J. Organic compounds of the alkali metals. In Comprehensive Organic Chemistry; Barton, D., Ollis, W.D., Eds.; Pergamon Press: Oxford, England, 1979; Vol. 3, Chapter 15.1;
14. (b) Negishi, E.I. Preparation of organolithiums and other organoalkali metals. Organometallics in Organic Synthesis; Wiley: New York, 1980; p. 96;
15. (c) Wakefield, B.J. Preparation of organolithium compounds. Organolithium Methods; Academic Press: London, 1988; Chapter 3;
16. (d) Ley, S.V.; Kouklovsky, C. Alkyl metals. In Comprehensive Organic Functional Group Transformations; Katritzky, A.R., Meth-Cohn, O., Rees, C.W., Eds.; Pergamon: Cambridge, England, 1995; Vol. 2, Chapter 2.11.
17. (a) Screttas, C.G.; Micha-Screttas, M. Hydrolithiation of α-olefins by a regiospecific two-step process. Transformation of alkyl phenyl sulfides to alkyllithium reagents. J. Org. Chem. 1978, 43, 1064.
18. (b) Screttas, C.G.; Micha-Screttas, M. Markownikoff two-step hydrolithiation of α-olefins. Transformation of secondary and tertiary alkyl phenyl sulfides to the relevant alkyllithium reagents. J. Org. Chem. 1979, 44, 713.
19. (c) Cohen, T.; Guo, B.-S. Reductive metallation. A general preparative method for hydrocarbon allylmetallic compounds. Tetrahedron 1986, 42, 2803;
20. (d) Screttas, C. G.; Smonou, I.C. Preparation of allylic lithium reagents with the allylic system partly incorporated into carbocyclic rings. J. Organomet. Chem. 1988, 342, 143;
21. (c) Cohen, T.; Bupathy, M. Organoalkali compounds by radical anion induced reductive metalation of phenyl thioethers. Acc. Chem. Res. 1989, 22, 152;
22. (d) Cohen, T.; Doubleday, M.D. A simple method for producing cycloalkenyl-lithiums from cycloalkanones via reductive lithiation of enol phenyl thioethers. J. Org. Chem. 1990, 55, 4784.
23. (a) Yus, M. Arena-catalyzed lithiation reactions. Chem. Soc. Rev. 1996, 25, 155;
24. (b) Ramón, D.J.; Yus, M. New methodologies based on arena-catalyzed lithiation reactions and their application to synthetic organic chemistry. Eur. J. Org. Chem. 2000, 225;
25. (c) Yus, M. From arena-catalyzed lithiation to other synthetic adventures. Synlett. 2001, 1197.
26. For a mechanistic study, see: (d) Yus, M.; Herrera, R.P.; Guijarro, A. On the mechanism of the naphthalene-catalysed lithiation: the role of the naphthalene dianion. Tetrahedron Lett. 2001, 42, 3455;
27. (e) Yus, M.; Herrera, R.P.; Guijarro, A. On the mechanism of arene-catalyzed lithiation: the role of arene dianions-naphthalene radical anion versus naphthalene dianion. Chem. Eur. J. 2002, 8, 2574.
28. For a polymer-supported version of this reaction, see: (a) Gómez, C.; Ruiz, S.; Yus, M. Polymer supported naphthalene-catalyzed lithiation reactions. Tetrahedron Lett. 1998, 39, 1397; (b) Gómez, C.; Ruiz, S.; Yus, M. Polymer supported arene-catalyzed lithiation reactions. Tetrahedron 1999, 55, 7017.
29. For a polymer-supported version of this reaction, see: (a) Gómez, C.; Ruiz, S.; Yus, M. Polymer supported naphthalene-catalyzed lithiation reactions. Tetrahedron Lett. 1998, 39, 1397; (b) Gómez, C.; Ruiz, S.; Yus, M. Polymer supported arene-catalyzed lithiation reactions. Tetrahedron 1999, 55, 7017.
30. For a review on the preparation of organolithium compounds from non-halogenated materials, see: Guijarro, D.; Yus, M. Non-deprotonating methodologies for organolithium reagents starting from non-halogenated materials. Recent Res. Dev. Org. Chem. 1998, 2, 713.
31. (a) Nájera, C.; Yus, M. Functionalized organo-lithium compounds in synthetic organic chemistry. Trends Org. Chem. 1991, 2, 155;
32. (b) Nájera, C.; Yus, M. Recent developments in the chemistry of functionalized organolithium compounds. Res. Dev. Org. Chem. 1997, 1, 67.
33. For a review on the preparation of organolithium compounds by ring opening of heterocycles, see: Yus, M.; Foubelo, F. Reductive opening of saturated oxa-, aza- and thia-cycles by means of an arene-promoted lithiation: synthetic applications. Rev. Heteroatom. Chem. 1997, 17, 73.
34. (a) Almena, J.; Foubelo, F.; Yus, M. Reductive opening of thiophthalan: a new route to functionalized sulfur-containing compounds. J. Org. Chem. 1996, 61, 1859;
35. (b) Almena, J.; Foubelo, F.; Yus, M. Reductive opening of phenyl substituted thiacycloalkanes: new way for sulfur-containing organolithium compounds. Tetrahedron 1997, 53, 5563;
36. (c) Yus, M.; Foubelo, F. DTBB-catalysed lithiation of 1,7-dihydrodibenzothiepin. Tetrahedron Lett. 2001, 42, 2469.
37. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
38. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
39. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
40. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
41. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
42. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
43. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
44. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
45. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
46. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
47. Via carbon-oxygen bond cleavage: (a) Guijarro, D.; Mancheño, B.; Yus, M. Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium. Tetrahedron 1992, 48, 4593; (b) Guijarro, D.; Mancheño, B.; Yus, M. Direct transformation of trialkyl phosphates into organo-lithium compounds by a DTBB-catalyzed lithiation. Tetrahedron 1994, 50, 8551; (c) Alonso, E.; Guijarro, D.; Yus, M. Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds. Tetrahedron 1995, 51, 11457; (d) Alonso, E.; Ramón, D.J.; Yus, M. Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules. J. Org. Chem. 1997, 62, 417; (e) Alonso, E.; Guijarro, D.; Martinez, P.; Ramón, D.J.; Yus, M. Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives. Tetrahedron 1999, 55, 11027; Via carbon-sulfur bond cleavage: (f) Guijarro, D.; Yus, M. Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones. Tetrahedron Lett. 1994, 35, 2965; (g) Alonso, E.; Guijarro, D.; Yus, M. Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums. Tetrahedron 1995, 51, 2699; Via reductive decyanation of nitriles: (h) Guijarro, D.; Yus, M. Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl in a barbier-type reaction. Tetrahedron 1994, 50, 3447; Via addition of lithium to double bonds: (i) Guijarro, D.; Mancheño, B.; Yus, M. C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles. Tetrahedron 1993, 49, 1327; (j) Guijarro, D.; Yus, M. Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols. Tetrahedron 1993, 49, 7761; (k) Yus, M.; Martinez, P.; Guijarro, D. DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents. Tetrahedron 2001, 57, 10119.
48. We have been able to trap the allylic and benzylic organolithium reagents generated by an arene catalyzed lithiation of allylic and benzylic chlorides (16a) and fluorides (16b) under Barbier type reaction conditions: (a) Gómez, C.; Huerta, F.F.; Yus, M. DTBB-catalyzed lithiation of chlorinated benzylic chlorides, alcohols, thiols or amines. Tetrahedron 1998, 54, 1853; (b) Guijarro, D.; Yus, M. Generation of allylic and benzylic organolithium compounds by fluorine- lithium exchange. J. Organomet. Chem. 2001, 624, 53.
49. We have been able to trap the allylic and benzylic organolithium reagents generated by an arene catalyzed lithiation of allylic and benzylic chlorides (16a) and fluorides (16b) under Barbier type reaction conditions: (a) Gómez, C.; Huerta, F.F.; Yus, M. DTBB-catalyzed lithiation of chlorinated benzylic chlorides, alcohols, thiols or amines. Tetrahedron 1998, 54, 1853; (b) Guijarro, D.; Yus, M. Generation of allylic and benzylic organolithium compounds by fluorine- lithium exchange. J. Organomet. Chem. 2001, 624, 53.
50. Kerr, J.A. Strengths of chemical bonds. In Handbook of Chemistry and Physics, 78th Ed.; Lide, D.R., Ed.; CRC Press: Boca Raton, USA, 1997; 9-51.
51. It has been reported that thiols and thiolates oxidize very easily to the corresponding disulfides even in an inert atmosphere. Zhang, Z.; Martell, A.E.; Motekaitis, R.J.; Fu, L. Synthesis of pentadentate mixed N/S dithiolate chelating ligands derived from heterocycles and 2-mercaptoethylamines. Tetrahedron Lett. 1999, 40, 4615.
52. For examples of the difference in regiochemistry in the reaction of geranyllithium with different electrophiles, see Ref.
53. (a) Bates, R.B.; Kroposki, L.M.; Potter, D.E. Cycloreversions of anions from tetrahydrofurans. Convenient synthesis of lithium enolates of aldehydes. J. Org. Chem. 1972, 37, 560;
54. (c) Mills, N.S.; Shapiro, J.; Hollingsworth, M. Dianions of 2-methyl-2-butene: evidence for the stability of a Y-aromatic species. J. Am. Chem. Soc. 1981, 103, 1263;
55. 3S}]. Chem. Commun. 2001, 1640.
56. (a) Monograph: Blomberg, C. The Barbier Reaction and Related One-Step Processes; Springer-Verlag: Berlin, Germany, 1993;
57. (b) Review: Alonso, F.; Yus, M. Review: Recent developments in Barbier-type reactions. Recent Res. Des. Org. Chem. 1997, 1, 397.
58. Watson, S.C.; Eastham, J.F. Colored indicators for simple direct titration of magnesium and lithium reagents. J. Organomet. Chem. 1967, 9, 165.
59. Nishio, T. Direct conversion of alcohols into thiols. J. Chem. Soc., Perkin Trans. 1 1993, 1113.
60. Mantegani, A.; Bonardi, G. Terpene compounds as drugs. XII. Activity of geranyl sulfur derivatives on experimental liver damages. Chim. Ther. 1972, 7, 411; Chem. Abstr. 1973, 78, 43727.
61. Mantegani, A.; Bonardi, G. Terpene compounds as drugs. XII. Activity of geranyl sulfur derivatives on experimental liver damages. Chim. Ther. 1972, 7, 411; Chem. Abstr. 1973, 78, 43727.
62. Barluenga, J.; Florez, J.; Yus, M. γ-Substituted secondary organo-alkaline compounds and their chlorinated precursors. Synthetic applications. Synthesis 1985, 846.