{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T19:40:13Z","timestamp":1790710813002,"version":"4.1.0"},"reference-count":70,"publisher":"Wiley","issue":"42","license":[{"start":{"date-parts":[[2016,10,6]],"date-time":"2016-10-06T00:00:00Z","timestamp":1475712000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2016,10,10]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Kinetically controlled catalytic cross\u2010metathesis reactions that generate (<jats:italic>Z<\/jats:italic>)\u2010\u03b1,\u03b2\u2010unsaturated esters selectively are disclosed. A key finding is that the presence of acetonitrile obviates the need for using excess amounts of a more valuable terminal alkene substrates. On the basis of X\u2010ray structure and spectroscopic investigations a rationale for the positive impact of acetonitrile is provided. Transformations leading to various E,Z\u2010dienoates are highly Z\u2010selective as well. Utility is highlighted by application to stereoselective synthesis of the C1\u2013C12 fragment of biologically active natural product (\u2212)\u2010laulimalide.<\/jats:p>","DOI":"10.1002\/anie.201608087","type":"journal-article","created":{"date-parts":[[2016,9,16]],"date-time":"2016-09-16T11:26:49Z","timestamp":1474025209000},"page":"13210-13214","source":"Crossref","is-referenced-by-count":34,"title":["Synthesis of Linear (<i>Z<\/i>)\u2010\u03b1,\u03b2\u2010Unsaturated Esters by Catalytic Cross\u2010Metathesis. The Influence of Acetonitrile"],"prefix":"10.1002","volume":"55","author":[{"given":"Elsie C.","family":"Yu","sequence":"first","affiliation":[{"name":"Department of Chemistry Merkert Chemistry Center Boston College  Chestnut Hill MA 02467 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Brett M.","family":"Johnson","sequence":"additional","affiliation":[{"name":"Department of Chemistry Merkert Chemistry Center Boston College  Chestnut Hill MA 02467 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Erik M.","family":"Townsend","sequence":"additional","affiliation":[{"name":"Department of Chemistry Massachusetts Institute of Technology  Cambridge MA 02139 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Richard R.","family":"Schrock","sequence":"additional","affiliation":[{"name":"Department of Chemistry Massachusetts Institute of Technology  Cambridge MA 02139 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amir H.","family":"Hoveyda","sequence":"additional","affiliation":[{"name":"Department of Chemistry Merkert Chemistry Center Boston College  Chestnut Hill MA 02467 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,10,6]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"For reviews regarding the development of kineticallyZ-selective olefin metathesis and their applications in organic synthesis see:"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200904491"},{"key":"e_1_2_2_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200904491"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1229713"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201300688"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo500467z"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527674107.ch21"},{"key":"e_1_2_2_7_1","unstructured":"For studies regarding CM reactions promoted by Ru-based complexes that generate predominantly (E)-\u03b1 \u03b2-unsaturated carbonyl compounds see:"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9939744"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja016386a"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.07.107"},{"key":"e_1_2_2_11_1","unstructured":"For catalyst-controlledZ-selective reactions catalyzed by Mo or W complexes and applications to synthesis of biologically active molecules see:"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature09957"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja403188t"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201302538"},{"key":"e_1_2_2_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201302538"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja509973r"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature17396"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaf4622"},{"key":"e_1_2_2_18_1","unstructured":"For catalyst-controlledZ-selective reactions catalyzed by Ru complexes see:"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja311916m"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206079"},{"key":"e_1_2_2_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206079"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4010267"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3SC52806E"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature14061"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b00031"},{"key":"e_1_2_2_25_1","unstructured":"For representative applications in complex molecule synthesis see:"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja980621g"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja011604l"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390322"},{"key":"e_1_2_2_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390293"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0609708"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200603656"},{"key":"e_1_2_2_30_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200603656"},{"key":"e_1_2_2_31_1","unstructured":"For example see:"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002356g"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0258428"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja028019k"},{"key":"e_1_2_2_35_1","first-page":"944","volume":"5","author":"Crimmins M. 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Drug Discovery Dev."},{"key":"e_1_2_2_36_1","unstructured":"For a review regarding application of six-membered lactone synthesis to preparation of laulimalide discussing certain difficult examples see:"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/1615-4169(200208)344:6\/7<573::AID-ADSC573>3.0.CO;2-C"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo010854h"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetasy.2007.10.006"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol101659y"},{"key":"e_1_2_2_41_1","unstructured":"\u00a0"},{"key":"e_1_2_2_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9719945"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)00158-1"},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601672"},{"key":"e_1_2_2_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja510768c"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja202818v"},{"key":"e_1_2_2_47_1","unstructured":"\u00a0"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature07594"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja902738u"},{"key":"e_1_2_2_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300576"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300576"},{"key":"e_1_2_2_51_1","unstructured":"It is unlikely that the alkylidene derived from 1-decene reacts with the kinetically formedZ-enoate to cause stereoisomerization; the corresponding all-syntrisubstituted metallacyclobutane intermediate would probably be energetically disfavored due to steric repulsion. For related discussions see: Ref.\u2005[4f]."},{"key":"e_1_2_2_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00123a023"},{"key":"e_1_2_2_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja020671s"},{"key":"e_1_2_2_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/om5002364"},{"key":"e_1_2_2_55_1","unstructured":"\u00a0"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00328-9"},{"key":"e_1_2_2_57_2","doi-asserted-by":"publisher","DOI":"10.1070\/RC2002v071n04ABEH000708"},{"key":"e_1_2_2_58_1","unstructured":"The comparatively lower yield ofZ-2\u2009hmight be partly the result of CM at the internalE-alkene. 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