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Gapinski, and R . R . Hutchins, J. Org. , 1979,44, 3599. T. Cohen and R . B. Weisenfeld, J. Org. , 1979, 44, 3601. ' 39 Aldehydes and Ketones R2 Reagents: i, Bu”Li; ii, Scheme 21 of reagent is thus available from a readily accessible oxidation state precursor, via a method which appears to be a useful complement to the deprotonation method. 90 liii 1 iii a-Lithiation of vinyl sulphides leads to anions which are synthetically equivalent to acyl anions. ” No allylic deprotonation was observed. The silicon-containing Grignard reagents (27) and (28) are alkylated in high The conversion of vinyl silanes via the yield in the presence of Cu’ epoxide into silyl enol prompts the recognition of these reagents as examples of the two nucleophilic synthons for acetaldehyde (Scheme 23).

Kawada, R. Okawara, S. Torii, and H. , 1979, 1045. I. Kuwajima and M. Kato, J. Chem. ,Chem. , 1979,708. A. P. Kozikowski and K . , 1979, 833. T. Hassel and D. Seebach, Angew. Chem. Int. Ed. , 1979,18, 399. M. -H. Geiss, and D. Seebach, Chem. , 1979, 112, 1420. E. Piers and H. E. Morton, J. Org. , 1979,44, 3437. C. G. M. Janssen, P. M. van Lier, H. M. Buck, and E. F. Godefroi, J. Org. , 1979,44,4199. ** CHO c o Reagents: i, Bu"Li; ii, MgBr,; iii, E+; iv, H,O+ Scheme 17 A RS M e 3 . &Me iii OH \ &Me R' R' 1 iv RdRIL Reagents: i, Base; ii, Me,C=CH-COR'; tHO R' 0 iii, KH iv, HgO; v, Base Scheme 18 Bu'Me,SiO SnMe, Bu'Me,SiO (21) SnMe, Bu'Me,SiO Li Reagents: i, [PhSCuSnMeJLi; ii, LDA-Bu'Me,SiCl; iii, MeLi; iv, E+; v, H,Ot Scheme 19 38 General and Synthetic Methods 411 ArSO, (22) Seebach has demonstrated the synthetic utility of the highly nucleophilic doubly reduced diene systems (23) and (24) as d 5 reagents.

Williams, J. Org. , 1979,44, 2955. M. Shimizu and I. , 1979, 2801. S. E. Jacobson, D. A. Muccigrosso, and F. Mares, J. Org. , 1979,44,921. M. Bertrand, G. Gil, and J. , 1979, 1595. ' D. H. R. Barton, D. J. Lester, W. B. Motherwell, and M. T. Barros Papoula, J. Chem. ,Chem. , 1979,705. ' C. Gundu Rao, S. U. Kulkarni, and H. C. Brown, J. Organomet. , 1979,172, C20. ' H. C. Brown, S. U. Kulkarni, and C. Gundu Rao, Synthesis, 1979, 702. Y. Tamura, Y. Yamamoto, Y. Yamada, and Z. , 1979, 1401. " Several references have appeared on the use of solid-phase oxidants.

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