{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,9]],"date-time":"2026-03-09T03:18:30Z","timestamp":1773026310587,"version":"3.50.1"},"reference-count":133,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2005,9,28]],"date-time":"2005-09-28T00:00:00Z","timestamp":1127865600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2006,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Ynolates were found to react with \u03b1\u2010alkoxy\u2010, \u03b1\u2010siloxy\u2010, and \u03b1\u2010aryloxyketones at room temperature to afford tetrasubstituted olefins with high <jats:italic>Z<\/jats:italic> selectivity. Since the geometrical selectivity was determined in the ring opening of the \u03b2\u2010lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high <jats:italic>Z<\/jats:italic> selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, \u03b1\u2010dialkylamino ketones provided olefins with excellent <jats:italic>Z<\/jats:italic> selectivity. These products can be easily converted into multisubstituted butenolides and \u03b3\u2010butyrolactams in good yield.<\/jats:p>","DOI":"10.1002\/chem.200500574","type":"journal-article","created":{"date-parts":[[2005,9,28]],"date-time":"2005-09-28T04:47:50Z","timestamp":1127882870000},"page":"524-536","source":"Crossref","is-referenced-by-count":41,"title":["Heteroatom\u2010Guided Torquoselective Olefination of \u03b1\u2010Oxy and \u03b1\u2010Amino Ketones via Ynolates"],"prefix":"10.1002","volume":"12","author":[{"given":"Mitsuru","family":"Shindo","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takashi","family":"Yoshikawa","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yasuaki","family":"Itou","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Seiji","family":"Mori","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takeshi","family":"Nishii","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kozo","family":"Shishido","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2005,12,19]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-08-052349-1.00020-2"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00094a007"},{"key":"e_1_2_6_3_2","first-page":"73","volume":"25","author":"Wadsworth W. S.","year":"1977","journal-title":"Org. React."},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b208078h"},{"key":"e_1_2_6_5_2","unstructured":"For reviews see:"},{"key":"e_1_2_6_6_2","first-page":"1","volume":"38","author":"Ager D. J.","year":"1990","journal-title":"Org. React."},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1991-20867"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/a908402i"},{"key":"e_1_2_6_9_2","unstructured":"For selected examples see:"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00479a061"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00173a035"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr980046z"},{"key":"e_1_2_6_13_2","first-page":"2763","author":"Hartley R. C.","year":"2000","journal-title":"J. Chem. Soc. Perkin Trans. 1"},{"key":"e_1_2_6_14_2","unstructured":"For recent examples of olefination of ketones leading to tetrasubstituted olefins see:"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)02135-9"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.50.1300"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo001760v"},{"key":"e_1_2_6_18_2","unstructured":"For example the Sharpless asymmetric epoxidation of trisubstituted allylic alcohols (tetrasubstituted olefins) provides the corresponding epoxides with high enantioselectivity. Since the products have contiguous asymmetric carbon atoms they would be useful for synthesis of natural products:"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00356a034"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00184a008"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0959-8049(99)00183-5"},{"key":"e_1_2_6_22_2","unstructured":"For recent examples see:"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja047169n"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0158229"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja027421w"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja970667u"},{"key":"e_1_2_6_27_2","unstructured":"For recent examples of stereoselective construction of tetrasubstituted olefins via carbometalation of alkynes 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[5] see:"},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00549566"},{"key":"e_1_2_6_103_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00177a012"},{"key":"e_1_2_6_104_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol990211c"},{"key":"e_1_2_6_105_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)00167-3"},{"key":"e_1_2_6_106_2","unstructured":"Gaussian\u200998 Revision\u2009A.11.3 M. J. Frisch G. W. Trucks H. B. Schlegel G. E. Scuseria M. A. Robb J. R. Cheeseman V. G. Zakrzewski J. A. Montgomery Jr. R. E. Stratmann J. C. Burant S. Dapprich J. M. Millam A. D. Daniels K. N. Kudin M. C. Strain O. Farkas J. Tomasi V. Barone M. Cossi R. Cammi B. Mennucci C. Pomelli C. Adamo S. Clifford J. Ochterski G. A. Petersson P. Y. Ayala Q. Cui K. Morokuma D. K. Malick A. D. Rabuck K. Raghavachari J. B. Foresman J. Cioslowski J. V. Ortiz A. G. Baboul B. B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R. Gomperts R. L. Martin D. J. Fox T. Keith M. A. Al\u2010Laham C. Y. Peng A. Nanayakkara C. Gonzalez M. Challacombe P. M. W. Gill B. Johnson W. Chen M. W. Wong J. L. Andres C. Gonzalez M. Head\u2010Gordon E. S. Replogle J. A. Pople Gaussian Inc. Pittsburgh PA 1998."},{"key":"e_1_2_6_107_2","unstructured":"NBO Version 5.0 implemented by E. D. Glendening A. E. Reed J. E. Carpenter F. Weinhold."},{"key":"e_1_2_6_108_2","unstructured":"If one assumes unsolvated pathways the chelated TSs are more stable than the nonchelated ones. 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