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The Enamine Alkylation and Acylation of Carbonyl Compounds

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The Enamine Alkylation and Acylation of Carbonyl Compounds Jan. N, 1963 ENAMINEALKYLATION AND ACYLATIONOF CARBONYLS 207 Sec. 2. Removal of Protecting Groups.-The conditions for treated with ninhydrin, then Feigl reagent,51 the latter reagent removal of the tert-butyl ether group were studied using the tert- showing the presence of a free SI<- group. Although all of the butyl esters of the tert-butoxyamino acids. Two drops of sample reagents except TFA yielded free cysteine, none of the reactions was treated with 3 drops of reagent. After an allotted time the went to completion. The latter reagent gave a product with an reaction was stopped by the addition of an excess of pyridine. Rfvalue of 0.70 which was positive to Feigl reagent. This has The results determined by chromatography of the reaction mix- been tentatively identified as H’cySH .O-t-Bu( L), since a spot ture either on Whatman h-0, 1 paper using the solvent system 1- which was ninhydrin positive with the same Ri value was found in butanol-acetic acid-water, 4: 1:5, (BAW), or on silica gel the startine base (ex. XX’I. plates (thin layer) using the solvent system sec-butyl alcohol- The Rf;slues of the cysteine derivatives in B.4M were deter- 37; ammonia, 3:1 (BAM). termined as: H.c~SH.OH(L), 0.05 H.cy(S-t-Buj .OH(L), Ex. A. Removal of teut-Butyl Groups from H.ser(0-t-Bu) .- 0.19; H.cy(S-t-Bu) ’ O-f-Bu( L), 0.72; H ’C~SH,0-t-Bu, 0.62. 0-t-Bu( DL) (III).-Using ninhydrin in butanol as the detecting Pure compounds were used, escept the last value was tentatively reagent, the Ri values in the B.4W system were: H.ser.OH- determined from a very weak ninhydrin-positive spot which (DL), 0.17; H.ser.0-l-B~(~~),0.70; H.ser(0-t-Bu.OH(~~) appeared in the distillate of the original preparation. This was 0.72; H.ser(O-t-Bu) .O-~-BU(DL)0.89. Since the second and eliminated if the base was initially purified as the hydrochloride third compounds could not be satisfactorily separated, the BAM salt. In addition to the previous reagents, three additional ones system was used. The results are shown in Table 111. were tested: hydrogen chloride in chloroform, hydrogen bromide in nitromethane and perchloric acid (7070) dissolved in glacial TABLEI11 acetic acid. X second perchloric acid treatment was continued for an hour. PRODUCTSFROM H.ser,(O-t-Bu).O-t-Bu(DL), RI VALUES(BAM) Development of color on the chromatograms by ninhydrin as €I.ser(O- well as subsequent treatment with chlorine and potassium iodide- II.ser(0-t- Hwr.0- t-Bu).O--t- tolidine reagent5*indicated that no reaction had gone to comple- Trcatnient at 23’ II*ser.OH Bu).OH t-Ru Bu tion. However, perchloric acid treatment for an hour gave 0.04 0.17 0.48 0.60 the best results with H crSH OH( Lj forming, and only one nin- Standards hydrin-positive spot remaining. This corresponded to H cp- HBr/IIOAc (5 niin.) .02 .I6 .48 .60 (S-t-Bu) . OH( L). An unidentified spot (tolidine positive) HI (57%) (5 min. j .05 .19 .46 .62 remained with an Rr of 0.39. HCl/CHC13 (5 min.) .04 .16 .44 .59 Ex. C. Removal of tevt-Butyl Groups from H . tyr( 0-t-Bu)- .O-t-Bu( L) (11).-The ester-ether was treated as areviouslv HBr/HOAc (30 min.) .04 described with hydrogen bromide in acetic acid, hidrobromic HCl/CHCla (30 min.) .03 .17 .53 .68 acid (407’), hydrogen chloride in chloroform, and @-toluenesul- foiiic acid. A11 reagents removed both tert-butyl groups. The Thus, the best method of removing both protecting groups BAW system was used, the spots being detected with ninhydrin; appears to be hydrogen bromide in acetic acid for a 30-minute RI0.59 for tyrosine and 0.94 for H.tyr(0-t-Bu) .O-~-BU(L). period. Ex. B. Removal of teut-Butyl Groups from H cy( S-t-Bu j. 0- Acknowledgment.-The authors wish to thank ilk. L. ~-Bu(L)(XX).-The Rf values in the BAW system for the ester- Brancone and his staff for the analyses and IClr. LV. thioether and related compounds were: HecySH. OH(L), 0.06; Fulmor and his staff for spectra and optical rotations. H.C~(S-~-BU).OH(L),0.78; H.cy(S-t-Bu).O-t-Bu(~), 0.89. The ester-thioether was treated, as described in ex. A, with per- (91) Fritz Feigl, “Qualitative Analysis of Spot Tests,” 2nd English Ed., chloric acid (io%), hydriodic acid (57%), hydriodic acid in acetic Sordeman Pub. Co , Inc., Xew York. S. T..1939, pp. 195 and 291. acid, and trifluoroacetic acid (TFA). The chromatograms were (92) F. Reindel and A. Hoppe, Be?,.,87, 1103 (1954). [CONTRIBUTIONFROM THE CHASDLERLABORATORIES OF COLUMBIAUNIVERSITY, SEW YORK 27, S. \-.I The Enamine Alkylation and Acylation of Carbonyl Compounds BY GILBERTSTORK, A. BRIZZOLARA,H. LANDESMAN,J. SZMUSZKOVICZ AND R. TERRELL RECEIVEDOCTOBER 5, 1962 The enamine alkylation and acylation of carbonyl compounds is discussed with regard to the preparation of enamines, their alkylation with electrophilic olefins, their alkylation with alkyl halides and finally their acylation with acid chlorides. This new synthetic method is remarkable by its mildness and by the ease with which mono- alkylation or acylation can be achieved. Introduction the reaction of the enolate derived from a carbonyl In 1954, we introduced a new and relatively general group with an electrophilic carbon (aldol, Claisen and synthetic method for the acylation and alkylation of related reactions, Alichael reaction, alkylation of metal carbonyl compounds.lS2 In the ensuing years the use- enolates, etc.; cf, B). fulness of the new reaction has been abundantly dem- onstrated by work in this Laboratory and elsewhere, and well over ninety papers have appeared since our initial p~blications.~A progress report on our own further work in this field has also been given.4 Our interest in devising new methods for the formation of ‘.Cf>> the carbon-carbon bond stems from the fact that there >OM + - $0 B is a relative scarcity of reactions that will accomplish this fundamental synthetic operation. In fact, a high Reactions of type B, although of considerable syn- proportion of the carbon-carbon-forming reactions of thetic importance, suffer from a number of serious interest in complex syntheses belong to two categories : limitations which we will illustrate using the alkylation the addition of a carbanion to a carbonyl group (aldol, of enolates and the related Michael reaction. Two Grignard, metal acetylide reactions, etc.; cf. A) and major difficulties are : (1) the necessity, particularly in the case of alkylation, of using a strong base (e.g., amide (1) G Stork, R. Terrell and J. Szmuszkovicz, J. Am. Chem. Soc., 76, 2029 (1954). ion, triphenylmethide ion, t-alkoxides) to transform the (2) G. Stork and H. Landesman, ibid., 78, 5128 (1956). carbonyl compound into its anion; (2) the proton trans- (3) The literature on enamines is reviewed in a chapter by J. Szmusz- fer reaction between the alkylated ketone formed in- kovicz in a forthcoming volume of “Advances in Organic Chemistry,” itially and the unreacted enolate ion. The first Interscience Publishers, Inc., Sew York, N. Y. (4) XVIth National Organic Symposium Abstracts, Seattle, Wash., problem is illustrated by, e.g., the self-condensation of June, 1959, pp. 44 ff. cyclopentanone by bases under conditions of the 20s G. STORK,A. BRIZZOLARA,H. LXNDESMAN.J. SZ~IUSZKOVICZ AND R. TERRELL VOl. s;, Claisen or Michael conden~ation,~the transformation the occurrence of this reaction had not been explored of 4-hydroxycyclohexanone benzoate into cyclopropane until our publication in spite of the fact that the neces- derivatives with &butoxide6and, of course, the well- sary enamines of ketones and aldehydes had been pre- known self-condensation of acetaldehyde and its mono- pared by a simple procedure, almost twenty years pre- substituted derivatives even with mild bases. The viously, by Mannich and Davidsen.lo This may well second problem may be illustrated by a typical ex- be due to the fact that apparently exclusive N-alkyla- ample : Attempted monoalkylation of 6-methoxy-P- tion had been recorded with a number of vinylamines. tetralone with one equivalent of methyl iodide in the For instance, reaction with methyl iodide converts presence of strong bases leads to almost no mono- neostrychnine’l (I) and the simpler dimethyltetra- methyl compound : a mixture of 6-methoxy-1,l-di- hydropyridine12 I1 into their respective N-methiodides. methyl-P-tetralone and recovered starting material is Similarly, the pyrrolidine enamine of testosterone (111) obtained instead.’ While this is perhaps an extreme has been shown to give very largely the “expected” case, this experience is very general and is a result of X-methiodide. l3 the rapid equilibration of enolates uiu proton transfers which take place under the usual alkylation conditions. The same difficulty is of course encountered in Michael addition reactions. Among many examples, one may fyy\ U CIIJO CHjO I I11 As is by now well known,14 we have found that the enamines of ketones (and of aldehydes in some cases) generally lead to predominant carbon alkylation and acylation. Since no base or other catalyst is needed for these reactions, the first of the two difficulties with the direct alkylation of carbonyl compounds is avoided. At the same time monoalkylation or acyla- tion is easily carried out, and the enamine alkylation or acylation is not beset by the second problem (poly- alkylation).
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