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Mechanism of Reaction of Carbon Monoxide with Phenyllithium'

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Mechanism of Reaction of Carbon Monoxide with Phenyllithium' lReprintedfrom the Journalof the AmericanChemical Society, 95,8118 (1973).] Copyright 1973by the American Chemical Societyand reprinted by permissionof the copyright owner. Mechanism of Reaction of Carbon Monoxide with Phenyllithium' Larry S. Trzupek, Terry L. Newirth,2 Edward G. Kelly, Norma Ethyl Sbarbati,sand George M. Whitesides* Contribution from the Department of Chemistry, MassachusettsInstitute of Technology,Cambridge, Massachusetts 02139. ReceiuedJuly 14, 1973 Abstract: The product mixtures obtained by reaction between phenyllithium and carbon monoxide in diethyl ether, followed by hydrolysis, include benzophenone (1). a,a-diphenylacetophenone(2), benzil (3), a,a-diphenyl- a-hydroxyacetophenone (4), benzpinacot (5), a-hydroxyacetophenone (6), 1,3,3-triphenylpropane-1,2-dione(7), 1,3,3-triphenylpropan-1-one-2,3-diol(8). and benzhydrol (9). Compounds 1, 2, 6,7, and 8 are produced in signifi- cant yields i 3,4,5, and 9 are produced in trace quantities. Spectroscopicstudies establish dilithium benzophenone dianion (18) as the first long-lived intermediate formed in this reaction; qualitative correlations betweenthe basicity of a number of organolithium reagentsand their reactivity toward carbon monoxide suggests,but does not prove, that benzoyllithium is a precursor of 18. Labeling experiments indicate that the products ultimately isolated following hydrolysis of the reaction mixture are derived from at least two pathways which compete for the initially formed 18. One involves combination of l8 with 1 equiv of phenyllithium and 1 equiv of carbon monoxide, followed by elimination of I equiv of lithium oxide. yielding 17, the lithium enolateof 2; a secondinvolves com- bination of 18 with 1 equiv of phenyllithium and 2 equiv of carbon monoxide. yielding 22,the trilithium trianion of 8. Hydrolysis of l7 yields 2 directly. Hydrolysis of 22 yields 8; reversealdol reactionsinvolving 8 or its pre- cursors generate1 and 6. The mechanism proposed to account for the major products of the reaction of phenyl- lithium and carbon monoxide is outlined in SchemeIII" On the basisof this scheme,plausible paths to the minor products of the reaction are proposed. he addition of nucleophilesto carbon monoxide, catalyzed oxidative coupling of amines with oarbon activated by coordination to metal ions, forms the monoxide,e and metal-catalyzedoxidation of carbon basisfor a thoroughly explored and useful class of re- monoxide in aqueoussolution,l0 each involve the attack actions. Transformationsrelated to the hydroformyla- of formally anionic groups on metal-coordinated tion process,4additions of organolithium reagents to carbon monoxide. Acylmetalliccompounds haveeither metal carbonyls,scarbonylation of mercury(ll) salts,6 been inferred or identified as intermediatesin many of organoboranes,Tand organocopper reagents,8metal- thesereactions, and this classof substanceprovides the foundation for discussionsof their mechanisms.l'5 (1) Supported by the National Institutes of Health, Grants GM 16020and HL-l5029, and by the U. S. Army ResearchOffice (Durham), The reactionsof nucleophileswith free or weakly co- Grant ARO-D-3 I -l 24-G69. ordinated carbon monoxide are less well understood. (2) National ScienceFoundation Trainee, 1968-1969. and (3) Fellow of the Consejo Nacional de InvestigacionesCientificas y Base-catalyzed carbonylation of alcohols Techrricas. | 965 -l 966. amines,11,12and the reactions of organolithium,r3 (4) M. Orchin and W. Rupilius,Cutal. Reu.,6,85(1972); J. Falbe, "Carbon Monoxide in Organic Synthesis,"C. R. Adams, translator, (9) W. Brackman, Discuss.Faraday Soc., No. 46, 122 (1968); K. Springer-Verlag,Berlin, 1970,and referencescited in each. I(ondo, N. Sonoda,and S.Tsutsumi, Chem.Lett.,373(1972). (5) E. O. Fischer,and A. Maasbijl, Chem. Ber., 10O,2445(1967), (10) A. C. Harknessand J. Halpern,J. Amer. Chem.Soc.,83, 1258 M. Ryang, L Rhee, and S. Tsutsumi, Bull. Chem. Soc. Jap.,37,341 (1961); S. Nakamura and J. Halpern, ibid.,83,4102(1961). (1964); S. I(. Myeong, Y. Sawa, M. Ryang, and S. Tsutsumi, ibld., (11) For examples,see H. Winteler, A. Bieler,and A. Guyer, Hela. 38, 330 (1965); W. F. Edgell, M. T. Yang, B. J. Bulkirr, R. Bayer.and Chim.Acta,37,237O ,1'954); J. Gjaldback,Acta Chem.Scand.,2.683 N. I{oizumi,J. Amer. Chem.9oc.,87,3080 (1965); D. J. Darensbourg, (1948)r R. Nast and P. Dilly, Angew. Chem.,Int. Ed. En91.,6,357 and M. Y. Darensbourg,Inorg. Chent.,9, 169l (1970); N{. Ryang, (1967). Organometal.Chem. Reu., Sect. A,5,67 (1970),and referencescited in (12) Thc reverse reaction, decarbonylation of formate esters and cach. formarnideswith base,has been examined by J. C. Powers,R. Seidner, (6) W. Schoeller,W. Schrauth,and W, Essers,Chent.Uer.,46,2864 f. G. Parsons,and H. J. Berwin,J. Org. Chem.,31,2623(1966). A (1913); T. C. W. Mak and J. Trotter, J. Chem. 9oc.,3243 (1962): formally related transformation, the McFadyen-Stcvens reaction, J. M. Davidson,,I.Chem. Soc. A,193 (1969). has been reviewcd by M. Sprecher,M. Feldkimel, and M. Wilchek, (7) M. E. D. Hillman, J. Amer. Chem.Soc., 84, 4715(1962); H. C. ibid.,26,3664(1961);M. S. Newman and E. G. Caflisch,J. Amer. Chem. Brown,Accounts Chem. Res.,2,65 (1969). Soc.,80, 862 (l 958). (8) J. Schwartz, TetrahedronLett.,2803 (1972). (13) M. Ryang and S. Tsutsumi,Bull. Chem.Soc. Jap.,34, 1341 Journal of the American Chemical Society I 95:24 I Nouember 28, 1973 81l9 -magnesium,11-17-sodium,18'le and -zinc2oreagents with benzene in pentane solution.28gave similar product carbon monoxide require nucleophilic attack on carbon distributionsbut were heterogeneousin the latter stages monoxide in the absenceof the obvious activation pro- of reaction. The quantity of carbon monoxide ab- vided by coordinating transition metal ions. Stabie sorbed when the reactionswere allowed to proceed to acyl derivatives of group Ia and IIa metal ions are not completionvaried with reactionconditions, but typically well-characterized entities, although they have been im- ca.0"8-1.0 equiv of carbonmonoxide was consumed per plicated in reactions betweencarbon monoxide and tert- equivalent of phenyllithium. butyllithiunl,2l trimethylsilyllithium,22 and various Hydrolysis and glpc analysisof the reaction mirtures lithium amides.23'24 led to identificationof a number of products: benzo- The work reported in this paper was initiated in the phenone(1), a.a-diphenylacetophenone(2). benzil (3). hope that a study of the reaction of carbon monoxide a.a-diphenyl-a-hydroxyacetophenone(4), and traces with phenyllithium would provide evidencebearing both of benzpinacol(5) and benzhydroi (9). Careful thin- on the stability of acyllithium compounds and on the layer chromatography of the nonvolatile products of mechanisms of the reactions between organometallic the hydrolysis permitted isolation of a-hydrox\aceto- derivativesof group [a and Ila metal ions and that it phenone(6) and two compoundsassigned the structures might suggest new approaches to the generation of 1.2,3-triphenyl-1,2-propanedione(7) and l.i.-1-triphe- nucleophilic acyl groups.25 In fact, no evidence for nyl-2,3-dihydroxy-1-propanone(8) on the basis t'ri eri- longJived acyllithiun compounds as intermediates in dence outlined below. Certain of these products. t)t this reaction has been obtained, although the existence oo of these substancesas transitory intermediates is sug- 1. CO(1 atm), Et'.,O ll il phl-i ---------------- PhcPh + PhccHPhz * gestedby certain of the data that follow. Nonetheless, 2'Hro thesedata establish the basic sequencesfollowed in the r z reaction between phenyllithium and carbon monoxide, o o ooH oHoH outline a number of interesting transformations involv- phc-Cphlllllll ing benzophenone ketyl, benzophenone dianion, and + PhCCPh2+ Ph2C-CPhr* 34s related materials, and suggestnew ways in which carbon monoxide might be used in synthesis. ooo ptr$cu,ou+ pn[ScnPhz* Results 67 Products. At -78o, phenyllithium in diethyl ether OOH OH OH solution reacts over ca.6 hr with carbon monoxide at I llll PhCCH-CPh,+ PhCHPhrl t reaction at 0o is complete in 3-4 hr. atm pressure; 89 The phenyllithium solutions used in most of the reac- tions in this study were obtained by reaction of bromo- their analogs,have beenreported in previousinvestiga- benzene with lithium metal and contained lithium tions of the reactions of carbon monoxide with marn bromide:26 the reactions of these solutions with carbon group organometallics.13-22 If reaction mixture S 3rc' monoxidewere homogeneousthroughout. Carbonyla- quenched with acetic anhydride before hydrolysis, onlr tion of analogous lithium halide free solutions of two major products are isolated: l-acetoxy-1,2,1-tri- phenyllithium, prepared by transmetallation of di- phenylethylene (10) and l-benzoyl-1-acetoxy-2'2-di- phenylmercury(I[) with lithium metal2T or by metal- phenylethylene (11). The combined yield of thesc' halogen exchange between r-butyllithium and iodo- o (1961); (1962)i Trsns. N. Y. Acad. 9ci.,27,724 (1965); Ph... 35, ll2l r c'o(r atm).Et,o '' ,Ph Ph-4 ,Ph Nippon Kagaku Zasshi, 82, 880 (1961); Chem. Abstr., 58' 12587b phli (l ):/ + tr< 963). 2AcrO / \ / \ (14) F. G. Fischer and O. Staffers,Justus Liebigs Ann. Chem.,500, AcO Ph AcO Ph 2s3 (1e33). (15) K. V. Puzitskii, Y. T. Eidus, and K. G. Ryabova, Izu. Akad. l0 1l Nazk SSSR,Ser. Khim., 1810(1966); Chem.Abstr.,66,9463lu(1967). (16) M. S. Kharasch and O. Reinmuth, "Grignard Reactions of materials is approximately 50-60/": 10 dominates at Nonmetallic Substances," Prentice-Hall, New York, N' Y., 1954, pp room temperature,Ll at low temperature. 910-9 13. 7 was prepared (17) M. Ryang and S. Tsutsumi, Nippon Kagaku Zasshi,82' 878 An authentic sample of compound (1961); Chem.Abstr.,58, 11387 (1963). using a scheme based on the directed aldol reaction2e (1964); (18) M. Schlosser,Angew. Chem.,Int. Ed. En91.,3,287 M. and in low yield by oxidation of 1,3,3-triphenyl-1- Ryang, H. Miyamoto, and S. Tsutsumi, Nippon Kagaku Zasshi, 82, 1276(1961);Chem.
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