Direct Transformation of Allylic and Benzylic Thiols, Thioethers, and Disulfides into Organolithium Compounds

References

• Barrett , G.C. 1979 . “ Thiols ” . In Comprehensive Organic Chemistry Edited by: Barton , D. and Ollis , W.D. Vol. 3 , Oxford, , England : Pergamon Press . Chapter 11.1
   Google Scholar
• Patai , S. 1974 . The Chemistry of the Thiol Group New York : Wiley .
   Google Scholar
• Ohno , A. and Oae , S. 1976 . Organic Chemistry of Sulphur Edited by: Oae , S. New York : Plenum .
   Google Scholar
• Sulphides. Ref.[1], Chapter 11.3
   Google Scholar
• Caubère , P. and Coutrot , P. 1991 . “ Reduction of sulfur–carbon bonds and of other heteroatoms bonded to tetrahedral carbon ” . In Comprehensive Organic Synthesis Edited by: Trost , B.M. and Fleming , I. Vol. 8 , 835 Oxford, , England : Pergamon .
   Google Scholar
• Larock , R.C. 1999 . “ Sulfur compounds ” . In Comprehensive Organic Transformations p. 53 New York : John Wiley & Sons .
   Google Scholar
• Oae , S. and Togo , H. 1981 . Facile conversion of aliphatic sulfonic acids, sulfinic acids, thiols, sulfonates, thiolsulfonates, and disulfides to the corresponding alkyl iodides by triphenylphosphine/iodine . Synthesis , : 371 For some examples of this transformation, see:
   Google Scholar
• Still , I.W.J. , Kutney , G.W. and McLean , D. 1982 . J. Convenient method for the conversion of thiols and disulfides to the corresponding chlorides . Org. Chem. , 47 : 560
   Web of Science ®Google Scholar
• Krafft , G.A. and Siddall , T.L. 1985 . Stereospecific displacement of sulfur from chiral centers. Activation via thiaphosphonium salts . Tetrahedron Lett. , 26 : 4867
   Google Scholar
• Pastor , S.D. and Hessell , E.T. 1985 . Substitution of unactivated aryl halides by thiolate anions in polyglymes . J. Org. Chem. , 50 : 4812
   Web of Science ®Google Scholar
• Barañano , D. and Hartwig , J.F. 1995 . Carbon–heteroatom bond–forming reductive elimination. Mechanism, importance of trapping reagents, and unusual electronic effects during formation of aryl sulfides . J. Am. Chem. Soc. , 117 : 2937
   Google Scholar
• Zheng , N. , McWilliams , J.C. , Fleitz , F.J. , Armstrong , III, J.D. and Volante , R.P. 1998 . Palladium–catalyzed synthesis of aryl sulfides from aryl triflates . J. Org. Chem. , 63 : 9606
   Web of Science ®Google Scholar
• Wakefield , B.J. 1979 . “ Organic compounds of the alkali metals ” . In Comprehensive Organic Chemistry Edited by: Barton , D. and Ollis , W.D. Vol. 3 , Oxford, , England : Pergamon Press . Chapter 15.1
   Google Scholar
• Negishi , E.I. 1980 . “ Preparation of organolithiums and other organoalkali metals ” . In Organometallics in Organic Synthesis p. 96 New York : Wiley .
   Google Scholar
• Wakefield , B.J. 1988 . “ Preparation of organolithium compounds ” . In Organolithium Methods London : Academic Press . Chapter 3
   Google Scholar
• Ley , S.V. and Kouklovsky , C. 1995 . “ Alkyl metals ” . In Comprehensive Organic Functional Group Transformations Edited by: Katritzky , A.R. , Meth-Cohn , O. and Rees , C.W. Vol. 2 , Cambridge, , England : Pergamon . Chapter 2.11
   Google Scholar
• Screttas , C.G. and Micha-Screttas , M. 1978 . Hydrolithiation of α-olefins by a regiospecific two-step process. Transformation of alkyl phenyl sulfides to alkyllithium reagents . J. Org. Chem. , 43 : 1064
   Web of Science ®Google Scholar
• Screttas , C.G. and Micha-Screttas , M. 1979 . Markownikoff two-step hydrolithiation of α-olefins. Transformation of secondary and tertiary alkyl phenyl sulfides to the relevant alkyllithium reagents . J. Org. Chem. , 44 : 713
   Web of Science ®Google Scholar
• Cohen , T. and Guo , B.-S. 1986 . Reductive metallation. A general preparative method for hydrocarbon allylmetallic compounds . Tetrahedron , 42 : 2803
   Google Scholar
• Screttas , C.G. and Smonou , I.C. 1988 . Preparation of allylic lithium reagents with the allylic system partly incorporated into carbocyclic rings . J. Organomet. Chem. , 342 : 143
   Google Scholar
• Cohen , T. and Bupathy , M. 1989 . Organoalkali compounds by radical anion induced reductive metalation of phenyl thioethers . Acc. Chem. Res. , 22 : 152
   Google Scholar
• Cohen , T. and Doubleday , M.D. 1990 . A simple method for producing cycloalkenyllithiums from cycloalkanones via reductive lithiation of enol phenyl thioethers . J. Org. Chem. , 55 : 4784
   Google Scholar
• Yus , M. 1996 . Arena-catalyzed lithiation reactions . Chem. Soc. Rev. , 25 : 155 For reviews, see:
   Google Scholar
• Ramón , D.J. and Yus , M. 2000 . New methodologies based on arena-catalyzed lithiation reactions and their application to synthetic organic chemistry . Eur. J. Org. Chem. , 225
   Google Scholar
• Yus , M. 2001 . From arena-catalyzed lithiation to other synthetic adventures . Synlett. , : 1197 For a mechanistic study, see:
   Google Scholar
• Yus , M. , Herrera , R.P. and Guijarro , A. 2001 . On the mechanism of the naphthalene-catalysed lithiation: the role of the naphthalene dianion . Tetrahedron Lett. , 42 : 3455
   Google Scholar
• Yus , M. , Herrera , R.P. and Guijarro , A. 2002 . On the mechanism of arene-catalyzed lithiation: the role of arene dianions-naphthalene radical anion versus naphthalene dianion . Chem. Eur. J. , 8 : 2574
   PubMedGoogle Scholar
• Gómez , C. , Ruiz , S. and Yus , M. 1998 . Polymer supported naphthalene-catalyzed lithiation reactions . Tetrahedron Lett. , 39 : 1397 For a polymer-supported version of this reaction, see:
   Google Scholar
• Gómez , C. , Ruiz , S. and Yus , M. 1999 . Polymer supported arene-catalyzed lithiation reactions . Tetrahedron , 55 : 7017
   Google Scholar
• Guijarro , D. and Yus , M. 1998 . Non-deprotonating methodologies for organolithium reagents starting from non-halogenated materials . Recent Res. Dev. Org. Chem. , 2 : 713 For a review on the preparation of organolithium compounds from non-halogenated materials, see:
   Google Scholar
• Nájera , C. and Yus , M. 1991 . Functionalized organolithium compounds in synthetic organic chemistry . Trends Org. Chem. , 2 : 155 For reviews, see:
   Google Scholar
• Nájera , C. and Yus , M. 1997 . Recent developments in the chemistry of functionalized organolithium compounds . Res. Dev. Org. Chem. , 1 : 67
   Google Scholar
• Yus , M. and Foubelo , F. 1997 . Reductive opening of saturated oxa-, aza- and thia-cycles by means of an arene-promoted lithiation: synthetic applications . Rev. Hetero-atom. Chem. , 17 : 73 For a review on the preparation of organolithium compounds by ring opening of heterocycles, see:
   Google Scholar
• Almena , J. , Foubelo , F. and Yus , M. 1996 . Reductive opening of thiophthalan: a new route to functionalized sulfur-containing compounds . J. Org. Chem. , 61 : 1859
   PubMedGoogle Scholar
• Almena , J. , Foubelo , F. and Yus , M. 1997 . Reductive opening of phenyl substituted thiacycloalkanes: new way for sulfur-containing organolithium compounds . Tetrahedron , 53 : 5563
   Google Scholar
• Yus , M. and Foubelo , F. 2001 . DTBB- catalysed lithiation of 1,7-dihydrodibenzothiepin . Tetrahedron Lett. , 42 : 2469
   Google Scholar
• Guijarro , D. , Mancheño , B. and Yus , M. 1992 . Naphthalene-catalyzed lithiation of allylic and benzylic mesylates: a new method for allyl-, methallyl-, and benzyllithium . Tetrahedron , 48 : 4593 Via carbon–oxygen bond cleavage:
   Google Scholar
• Guijarro , D. , Mancheño , B. and Yus , M. 1994 . Direct transformation of trialkyl phosphates into organolithium compounds by a DTBB-catalyzed lithiation . Tetrahedron , 50 : 8551
   Google Scholar
• Alonso , E. , Guijarro , D. and Yus , M. 1995 . Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds . Tetrahedron , 51 : 11457
   Google Scholar
• Alonso , E. , Ramón , D.J. and Yus , M. 1997 . Simple synthesis of 5-substituted resorcinols: a revisited family of interesting bioactive molecules . J. Org. Chem. , 62 : 417
   PubMed Web of Science ®Google Scholar
• Alonso , E. , Guijarro , D. , Martinez , P. , Ramón , D.J. and Yus , M. 1999 . Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate, and urea derivatives . Tetrahedron , 55 : 11027
   Google Scholar
• Guijarro , D. and Yus , M. 1994 . Naphthalene-catalyzed reductive desulfonylation with lithium: alkyllithiums from alkyl phenyl sulfones . Tetrahedron Lett. , 35 : 2965 Via carbon–sulfur bond cleavage:
   Google Scholar
• Alonso , E. , Guijarro , D. and Yus , M. 1995 . Arene-catalyzed reductive desulfonylation and desulfinylation reactions: new routes for alkyllithiums . Tetrahedron , 51 : 2699
   Google Scholar
• Guijarro , D. and Yus , M. 1994 . 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 , 50 : 3447 Via reductive decyanation of nitriles:
   Google Scholar
• Guijarro , D. , Mancheño , B. and Yus , M. 1993 . C,O-dilithiated diarylmethanols: easy and improved preparation by naphthalene-catalyzed lithiation of diaryl ketones and reactivity toward electrophiles . Tetrahedron , 49 : 1327 Via addition of lithium to double bonds:
   Google Scholar
• Guijarro , D. and Yus , M. 1993 . Naphthalene-catalyzed lithiation of phenone imines in the presence of carbonyl compounds: preparation of 1,2-amino alcohols . Tetrahedron , 49 : 7761
   Google Scholar
• Yus , M. , Martinez , P. and Guijarro , D. 2001 . DTBB-catalysed dilithiation of styrene and its methyl-derivatives: introduction of two electrophilic reagents . Tetrahedron , 57 : 10119
   Google Scholar
• Gómez , C. , Huerta , F.F. and Yus , M. 1998 . DTBB-catalyzed lithiation of chlorinated benzylic chlorides, alcohols, thiols or amines . Tetrahedron , 54 : 1853 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:
   Google Scholar
• Guijarro , D. and Yus , M. 2001 . Generation of allylic and benzylic organolithium compounds by fluorine-lithium exchange . J. Organomet. Chem. , 624 : 53
   Google Scholar
• Kerr , J.A. 1997 . “ Strengths of chemical bonds ” . In Handbook of Chemistry and Physics, , 78th Ed. Edited by: Lide , D.R. 9 – 51 . Boca Raton, , USA : CRC Press .
   Google Scholar
• Zhang , Z. , Martell , A.E. , Motekaitis , R.J. and Fu , L. 1999 . Synthesis of pentadentate mixed N/S dithiolate chelating ligands derived from heterocycles and 2-mercaptoethylamines . Tetrahedron Lett. , 40 : 4615 It has been reported that thiols and thiolates oxidize very easily to the corresponding disulfides even in an inert atmosphere
   Web of Science ®Google Scholar
• For examples of the difference in regiochemistry in the reaction of geranyllithium with different electrophiles, see Ref.[15c] [15e] [16b]
   Google Scholar
• Bates , R.B. , Kroposki , L.M. and Potter , D.E. 1972 . Cycloreversions of anions from tetrahydrofurans. Convenient synthesis of lithium enolates of aldehydes . J. Org. Chem. , 37 : 560
   Web of Science ®Google Scholar
• Mills , N.S. , Shapiro , J. and Hollingsworth , M. 1981 . Dianions of 2-methyl-2-butene: evidence for the stability of a Y-aromatic species . J. Am. Chem. Soc. , 103 : 1263
   Google Scholar
• Walfort , B. , Pandey , S.K. and Stalke , P. 2001 . The inverse podant [Li3{(NBut)3S}]+ stabilises a single ethylene oxide OCH=CH2 anion as a high- and low-temperature polymorph of [(THF)3Li3(OCH=CH2){(NBut)3S}] . Chem. Commun. , : 1640
   PubMedGoogle Scholar
• Blomberg , C. 1993 . The Barbier Reaction and Related One - Step Processes Berlin, , Germany : Springer-Verlag . Monograph:
   Google Scholar
• Alonso , F. and Yus , M. 1997 . Review: Recent developments in Barbier-type reactions . Recent Res. Des. Org. Chem. , 1 : 397 Review
   Google Scholar
• Watson , S.C. and Eastham , J.F. 1967 . Colored indicators for simple direct titration of magnesium and lithium reagents . J. Organomet. Chem. , 9 : 165
   Web of Science ®Google Scholar
• Nishio , T. 1993 . Direct conversion of alcohols into thiols . J. Chem. Soc., Perkin Trans. 1 , : 1113
   Google Scholar
• Mantegani , A. and Bonardi , G. 1972 . Terpene compounds as drugs. XII. Activity of geranyl sulfur derivatives on experimental liver damages . Chim. Ther. , 7 : 411 Chem. Abstr. 1973, 78 43727
   Google Scholar
• Barluenga , J. , Florez , J. and Yus , M. 1985 . γ-Substituted secondary organoalkaline compounds and their chlorinated precursors . Synthetic applications. Synthesis , : 846
   Google Scholar