{"title":"Kinetic resolution of racemic planar-chiral vinylcymantrenes by molybdenum-catalyzed asymmetric metathesis dimerization.","authors":"Haruna Imazu, Hitoshi Izu, Yasuhiro Ohki, Masamichi Ogasawara","doi":"10.3762/bjoc.22.42","DOIUrl":null,"url":null,"abstract":"<p><p>Highly diastereo- and enantioselective kinetic resolution (KR) of a series of racemic planar-chiral 1-R-2-vinylcymantrenes (<i>rac</i>-<b>1</b>; R = Br, Me, I) was realized by an asymmetric metathesis dimerization (AMD) reaction catalyzed by a chiral molybdenum-alkylidene precatalyst. The Mo/(<i>R</i>)-<b>L1</b> precatalyst promoted the AMD/KR reaction of <i>rac</i>-<b>1a</b> (R = Br) to give (<i>E</i>)-(<i>R</i>,<i>R</i>)-<b>2a</b> of 99% ee together with unreacted recovered (<i>S</i>)-<b>1a</b> of 45% ee at 37% conversion. The diastereoselectivity of this reaction was excellent with <i>chiral</i>-<b>2a</b>/<i>meso</i>-<b>2a</b> = 96:4 molar ratio, and the selectivity factor (<i>k</i> <sub>rel</sub>) was calculated to be 754 based on a second-order equation. In all the three substrates examined, the dimerized products, <i>chiral</i>-<b>2</b>, were obtained in >98% ee thanks to the outstanding enantioselectivity.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"568-574"},"PeriodicalIF":2.7000,"publicationDate":"2026-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13058277/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Beilstein Journal of Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3762/bjoc.22.42","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2026/1/1 0:00:00","PubModel":"eCollection","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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Abstract
Highly diastereo- and enantioselective kinetic resolution (KR) of a series of racemic planar-chiral 1-R-2-vinylcymantrenes (rac-1; R = Br, Me, I) was realized by an asymmetric metathesis dimerization (AMD) reaction catalyzed by a chiral molybdenum-alkylidene precatalyst. The Mo/(R)-L1 precatalyst promoted the AMD/KR reaction of rac-1a (R = Br) to give (E)-(R,R)-2a of 99% ee together with unreacted recovered (S)-1a of 45% ee at 37% conversion. The diastereoselectivity of this reaction was excellent with chiral-2a/meso-2a = 96:4 molar ratio, and the selectivity factor (krel) was calculated to be 754 based on a second-order equation. In all the three substrates examined, the dimerized products, chiral-2, were obtained in >98% ee thanks to the outstanding enantioselectivity.
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