{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T18:46:29Z","timestamp":1792176389453,"version":"4.4.0"},"reference-count":80,"publisher":"Wiley","issue":"48","license":[{"start":{"date-parts":[[2014,10,6]],"date-time":"2014-10-06T00:00:00Z","timestamp":1412553600000},"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":[[2014,11,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl\u2010derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one\u2010carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all\u2010carbon or heteroatom\u2010substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four\u2010carbon coupling partner is not the turnover\u2010limiting step of the catalytic cycle.<\/jats:p>","DOI":"10.1002\/anie.201405854","type":"journal-article","created":{"date-parts":[[2014,10,6]],"date-time":"2014-10-06T21:30:03Z","timestamp":1412631003000},"page":"13183-13187","source":"Crossref","is-referenced-by-count":121,"title":["Biphenyl\u2010Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes"],"prefix":"10.1002","volume":"53","author":[{"given":"Daniel T.","family":"Ziegler","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lorena","family":"Riesgo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takuya","family":"Ikeda","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuji","family":"Fujiwara","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregory C.","family":"Fu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,10,6]]},"reference":[{"key":"e_1_2_2_1_2","volume-title":"Phosphorus Ligands in Asymmetric Catalysis","year":"2008"},{"key":"e_1_2_2_2_2","unstructured":"For pioneering studies see:"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo951661v"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9644687"},{"key":"e_1_2_2_5_2","unstructured":"For reviews see:"},{"key":"e_1_2_2_6_2","first-page":"723","author":"Fan Y. C.","year":"2012","journal-title":"Science of Synthesis Asymmetric Organocatalysis, Vol.\u20051"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527211798109222"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0029-1219157"},{"key":"e_1_2_2_9_2","first-page":"1175","volume-title":"Phosphorus Ligands in Asymmetric Catalysis, Vol.\u20053","author":"Gr\u00f6ger H.","year":"2008"},{"key":"e_1_2_2_10_2","unstructured":"These phosphepines were originally developed as ligands for transition\u2010metal\u2010catalyzed processes:"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0957-4166(94)80005-7"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460190"},{"key":"e_1_2_2_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200460190"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00164c"},{"key":"e_1_2_2_14_2","unstructured":"For initial reports of the use of these phosphepines as chiral nucleophilic catalysts see:"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja053277d"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503312"},{"key":"e_1_2_2_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200503312"},{"key":"e_1_2_2_17_2","unstructured":"For an overview of subsequent work by us and by others see Ref.\u2005[4c]."},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201000252"},{"key":"e_1_2_2_19_2","unstructured":"For recent overviews see:"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc47368f"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CC15793K"},{"key":"e_1_2_2_22_2","unstructured":"\u00a0"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.2174\/13852728113176660150"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1572-5995(03)80013-3"},{"key":"e_1_2_2_25_2","unstructured":"For the pioneering development of racemic processes see:"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00114a048"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)02405-8"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000253x"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo026111t"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo034281f"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390266"},{"key":"e_1_2_2_31_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390241"},{"key":"e_1_2_2_32_2","unstructured":"For early examples of enantioselective variants see:"},{"key":"e_1_2_2_33_2","unstructured":"Ref.\u2005[2b];"},{"key":"e_1_2_2_34_2","unstructured":"Ref.\u2005[5b]."},{"key":"e_1_2_2_35_2","volume-title":"Quaternary Stereocenters: Challenges and Solutions for Organic Synthesis","year":"2005"},{"key":"e_1_2_2_36_2","unstructured":"For early examples see:"},{"key":"e_1_2_2_37_2","unstructured":"Ref.\u2005[5b];"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo062170l"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0734243"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja806060a"},{"key":"e_1_2_2_41_2","unstructured":"For exceptions (\u226570\u2009%ee) see:"},{"key":"e_1_2_2_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000446"},{"key":"e_1_2_2_42_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201000446"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1106282"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja2049012"},{"key":"e_1_2_2_45_2","first-page":"2003","author":"Neel M.","year":"2011","journal-title":"Synthesis"},{"key":"e_1_2_2_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201302045"},{"key":"e_1_2_2_46_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201302045"},{"key":"e_1_2_2_47_2","unstructured":"Reference\u2005[13c]."},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja100432m"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34619b"},{"key":"e_1_2_2_50_2","unstructured":"For a few other early examples of non\u2010enantioselective phosphine\u2010catalyzed [4+1] annulations see:"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201000193"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol101611v"},{"key":"e_1_2_2_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo201802p"},{"key":"e_1_2_2_54_2","unstructured":"For example see:"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja963835b"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar030051b"},{"key":"e_1_2_2_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja307425g"},{"key":"e_1_2_2_58_2","unstructured":"Reference\u2005[5]."},{"key":"e_1_2_2_59_2","unstructured":"\u201cChiral Phosphine\u2010Catalyzed Asymmetric [4+1] Annulations of 2\u2010(Acetoxymethyl)buta\u20102 3\u2010dienoates with 1 1\u2010Bisnucleophiles\u201d: D.\u2005T. Ziegler G.\u2005C. Fu Abstracts of Papers 244th ACS National Meeting Philadelphia PA Aug 19\u201323 2012 ORGN 35. The investigation was completed in 2013."},{"key":"e_1_2_2_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201311214"},{"key":"e_1_2_2_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201311214"},{"key":"e_1_2_2_61_2","unstructured":"For reviews of bioactive compounds\/natural products which include a cyano group see:"},{"key":"e_1_2_2_62_2","doi-asserted-by":"publisher","DOI":"10.1039\/a804370a"},{"key":"e_1_2_2_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm100762r"},{"key":"e_1_2_2_64_2","volume-title":"Science of Synthesis, Vol.\u200519","year":"2004"},{"key":"e_1_2_2_65_2","unstructured":"Although we have not yet pursued systematic studies of 3 3\u2032\u2010substituted biphenyl\u2010derived phosphepines our investigations of binaphthyl\u2010based phosphepines suggest that the substituted aromatic groups in the 3\u2010 and 3\u2032\u2010positions may play a significant role in enhancing enantioselectivity."},{"key":"e_1_2_2_66_2","unstructured":"Exposure of (R)\u20103and (R)\u20104(as solids) to air for 21\u2005days led to essentially no phosphine oxide (<5\u2009%) according to31P\u2005NMR spectroscopy. Exposure of toluene solutions to air for 8\u2005days led to about 10\u2009% oxidation of (R)\u20103and about 55\u2009% oxidation of (R)\u20104."},{"key":"e_1_2_2_67_2","unstructured":"Notes:"},{"key":"e_1_2_2_68_2","unstructured":"On a gram\u2010scale the reaction illustrated in Table\u20052 entry\u20051 proceeded in 93\u2009%eeand 76\u2009% yield (1.12\u2005g) with 88\u2009% recovery of the catalyst as the phosphine oxide (after oxidation withtBuOOH);"},{"key":"e_1_2_2_69_2","unstructured":"The absolute configurations of eight of the [4+1] annulation products described herein were determined by X\u2010ray crystallography (see the Supporting Information)."},{"key":"e_1_2_2_70_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2013.01.054"},{"key":"e_1_2_2_71_2","unstructured":"Under our standard reaction conditions n\u2010hexylsulfonylacetonitrile undergoes this [4+1] annulation in 78\u2009%eeand 94\u2009% yield (determined by1H\u2005NMR spectroscopy with the aid of an internal standard)."},{"key":"e_1_2_2_72_2","unstructured":"Notes:"},{"key":"e_1_2_2_73_2","unstructured":"The minor diastereomer is formed in 28\u2009%\u2005ee;"},{"key":"e_1_2_2_74_2","unstructured":"We have not yet examined the impact of the choice of ester on theee d.r. and yield."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201405854","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201405854","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,16]],"date-time":"2023-10-16T20:05:47Z","timestamp":1697486747000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201405854"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,10,6]]},"references-count":80,"journal-issue":{"issue":"48","published-print":{"date-parts":[[2014,11,24]]}},"alternative-id":["10.1002\/anie.201405854"],"URL":"https:\/\/doi.org\/10.1002\/anie.201405854","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,10,6]]}}}