{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T22:04:16Z","timestamp":1790460256930,"version":"4.1.0"},"reference-count":20,"publisher":"American Chemical Society (ACS)","issue":"19","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Am. Chem. 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Chem.1989,181,\u2009(up to 17% ee)","DOI":"10.1002\/jlac.198919890135"},{"key":"ref3\/cit3b","unstructured":"bDehmlow, E. V. and Sauerbier, C.Pol. J. Chem.1994,68,2199,\u2009(up to 4% ee)."},{"key":"ref4\/cit4","doi-asserted-by":"crossref","first-page":"2027","DOI":"10.1039\/b704542e","volume":"5","author":"Shibasaki M.","year":"2007","journal-title":"Org. Biomol. Chem."},{"key":"ref5\/cit5","doi-asserted-by":"crossref","unstructured":"For the catalytic enantioselective cyanosilylation of ketones using Gd-2, see:Yabu, K., Masumoto, S., Yamasaki, S., Hamashima, Y., Kanai, M., Du, W., Curran, D. P., and Shibasaki, M.J. Am. Chem. Soc.2001,123,9908.","DOI":"10.1021\/ja016682n"},{"key":"ref6\/cit6a","doi-asserted-by":"crossref","first-page":"568","DOI":"10.1055\/s-1997-3235","author":"Kitajima H.","year":"1997","journal-title":"Synlett"},{"key":"ref6\/cit6b","doi-asserted-by":"crossref","first-page":"1994","DOI":"10.1021\/ja983864h","volume":"121","author":"Evans D. A.","year":"1999","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7","unstructured":"In the previous catalytic enantioselective conjugate addition of cyanide to \u03b1,\u03b2-unsaturatedN-acylpyrroles (ref2b), use of a slight excess of TMSCN to DMP was critical for high catalyst turnover and enantioselectivity, and the conditions of TMSCN:DMP = 1:1 were not effective. On the other hand, application of the previous conditions (2.5 equiv of TMSCN and 2 equiv of DMP) to the cyanation of enones resulted in partial formation of TMS-protected cyanohydrin (9a\/TMS-10a= 75\/25 in 65% combined yield at room temp). For detailed comparison between the previous and present reaction conditions (i.e., effects of the remaining TMSCN), seeSupporting Information."},{"key":"ref8\/cit8","first-page":"255","volume":"25","author":"Nagata W.","year":"1977","journal-title":"Org. React."},{"key":"ref9\/cit9","unstructured":"DMP was completely silylated based on TLC analysis."},{"key":"ref10\/cit10","unstructured":"SeeSupporting Informationfor details."},{"key":"ref11\/cit11","doi-asserted-by":"crossref","first-page":"16438","DOI":"10.1021\/ja067003h","volume":"128","author":"Fujimori I.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref12\/cit12","unstructured":"Consistent with this hypothesis, preincubation of the Gd complex with a catalytic amount of TBSCN (10 mol %) produced markedly improved 1,4-selectivity (93\/7) using TMSCN + DMP (1:1) as the cyanation reagent at \u221220 \u00b0C (cf. Table1, entry 5). For further experimental support for this hypothesis, seeSupporting Information."},{"key":"ref13\/cit13","doi-asserted-by":"crossref","first-page":"14158","DOI":"10.1021\/ja076346s","volume":"129","author":"Nishimura T.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref14\/cit14","unstructured":"On the other hand, TMS cyanohydrins were intact."},{"key":"ref15\/cit15","doi-asserted-by":"crossref","first-page":"7439","DOI":"10.1021\/ja071512h","volume":"129","author":"Oisaki K.","year":"2007","journal-title":"J. Am. Chem. 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