{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T23:38:00Z","timestamp":1792021080651,"version":"4.4.0"},"reference-count":112,"publisher":"Wiley","issue":"37","license":[{"start":{"date-parts":[[2018,7,24]],"date-time":"2018-07-24T00:00:00Z","timestamp":1532390400000},"content-version":"am","delay-in-days":365,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2017,7,24]],"date-time":"2017-07-24T00:00:00Z","timestamp":1500854400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-SC0001057"],"award-info":[{"award-number":["DE-SC0001057"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2017,9,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>This Review brings a new perspective to the study of chemical reactions in compressed fluid media. We begin by reviewing the substantial insight gained from more than 50\u2005years of experimental studies on organic reactions in solution under pressure. These led to a proper estimation of the critical roles of volume of activation (\u0394<jats:sup>\u2260<\/jats:sup>V) and reaction volume (\u0394V) in understanding pressure effect on rates and equilibria of organic reactions. A recently developed computational method, the XP\u2010PCM (extreme pressure polarizable continuum model) method, capable of carrying out quantum mechanical calculations of reaction pathways of molecules under pressure, is introduced. A case study of the Diels\u2013Alder cycloaddition of cyclopentadiene with ethylene serves, in pedagogical detail, to describe the methodology. We then apply the XP\u2010PCM method to a selection of other pericyclic reactions, including the parent Diels\u2013Alder cycloaddition of butadiene with ethylene, electrocyclic ring\u2010opening of cyclobutene, electrocyclic ring\u2010closing of Z\u2010hexatriene, the [1,5]\u2010H shift in Z\u2010pentadiene, and the Cope rearrangement. These serve as examples of some of the most common combinations of \u0394<jats:sup>\u2260<\/jats:sup>V and \u0394V. Interesting phenomena such as a shift in a transition state along a reaction coordinate, a switch of rate\u2010determining step, and the possible turning of a transition state into a stable minimum are revealed by the calculations. A reaction volume profile, the change in the volume of the reacting molecules as the reaction proceeds, emerges as being useful.<\/jats:p>","DOI":"10.1002\/anie.201705427","type":"journal-article","created":{"date-parts":[[2017,7,24]],"date-time":"2017-07-24T23:51:48Z","timestamp":1500940308000},"page":"11126-11142","source":"Crossref","is-referenced-by-count":136,"title":["The Effect of Pressure on Organic Reactions in Fluids\u2014a New Theoretical Perspective"],"prefix":"10.1002","volume":"56","author":[{"given":"Bo","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology, Baker Laboratory Cornell University  Ithaca NY 14853-1301 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5369-6046","authenticated-orcid":false,"given":"Roald","family":"Hoffmann","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, Baker Laboratory Cornell University  Ithaca NY 14853-1301 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7026-7750","authenticated-orcid":false,"given":"Roberto","family":"Cammi","sequence":"additional","affiliation":[{"name":"Department of Chemical Science, Life Science and Environmental Sustainability University of Parma  Viale Parco Area delle Scienze. 17\/a Parma 43100 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2017,7,24]]},"reference":[{"key":"e_1_2_10_1_1","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1002\/9780470171844.ch3","volume-title":"Progress in Physical Organic Chemistry","author":"Le Noble W. J.","year":"1967"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60314a004"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00093a005"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr970461b"},{"key":"e_1_2_10_5_1","volume-title":"High Pressure Chemistry","year":"2002"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/b515964b"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/tf9353100875"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1749604"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1351\/pac199466051077"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-009-3827-4_12"},{"key":"e_1_2_10_11_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-011-4669-2_18"},{"key":"e_1_2_10_12_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-011-1699-2_19"},{"key":"e_1_2_10_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.199719970404"},{"key":"e_1_2_10_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527612628.ch08"},{"key":"e_1_2_10_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/i200032a001"},{"key":"e_1_2_10_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-015-8295-7_18"},{"key":"e_1_2_10_17_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-015-8295-7_19"},{"key":"e_1_2_10_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/aic.690410712"},{"key":"e_1_2_10_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527613687"},{"key":"e_1_2_10_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar040082m"},{"key":"e_1_2_10_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/a805536j"},{"key":"e_1_2_10_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9700989"},{"key":"e_1_2_10_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/9780470148136"},{"key":"e_1_2_10_24_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.3.153"},{"key":"e_1_2_10_25_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat4088"},{"key":"e_1_2_10_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.nanolett.5b01343"},{"key":"e_1_2_10_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b09053"},{"key":"e_1_2_10_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527612628.ch02"},{"key":"e_1_2_10_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3897(200009)342:7<609::AID-PRAC609>3.0.CO;2-Z"},{"key":"e_1_2_10_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/0470857218.ch12"},{"key":"e_1_2_10_31_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.47.2242"},{"key":"e_1_2_10_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197501371"},{"key":"e_1_2_10_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19750870603"},{"key":"e_1_2_10_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.24206"},{"key":"e_1_2_10_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9904009"},{"key":"e_1_2_10_35_1","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(90)80002-F"},{"key":"e_1_2_10_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602485"},{"key":"e_1_2_10_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602485"},{"key":"e_1_2_10_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp9621991"},{"key":"e_1_2_10_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60304a002"},{"key":"e_1_2_10_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100317a048"},{"key":"e_1_2_10_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100167a032"},{"key":"e_1_2_10_41_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_10_42_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_10_43_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF00533485"},{"key":"e_1_2_10_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp035501w"},{"key":"e_1_2_10_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00072a001"},{"key":"e_1_2_10_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100785a001"},{"key":"e_1_2_10_47_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.bb.06.060177.001055"},{"key":"e_1_2_10_48_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4757285"},{"key":"e_1_2_10_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp504173k"},{"key":"e_1_2_10_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct5011517"},{"key":"e_1_2_10_51_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.30.9.244"},{"key":"e_1_2_10_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198008413"},{"key":"e_1_2_10_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19800921105"},{"key":"e_1_2_10_53_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-011-1699-2_18"},{"key":"e_1_2_10_54_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2005.01.126"},{"key":"e_1_2_10_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01607a027"},{"key":"e_1_2_10_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527612628.ch04"},{"key":"e_1_2_10_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.7b02805"},{"key":"e_1_2_10_58_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196907811"},{"key":"e_1_2_10_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19690812102"},{"key":"e_1_2_10_59_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(78)88134-4"},{"key":"e_1_2_10_60_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(98)83012-3"},{"key":"e_1_2_10_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199206821"},{"key":"e_1_2_10_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921040606"},{"key":"e_1_2_10_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp984710r"},{"key":"e_1_2_10_63_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199410791"},{"key":"e_1_2_10_63_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19941061008"},{"key":"e_1_2_10_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja973936p"},{"key":"e_1_2_10_65_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200352853"},{"key":"e_1_2_10_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200352853"},{"key":"e_1_2_10_66_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1677221"},{"key":"e_1_2_10_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100244a058"},{"key":"e_1_2_10_68_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.69.462"},{"key":"e_1_2_10_69_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.273.5272.218"},{"key":"e_1_2_10_70_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.78.4446"},{"key":"e_1_2_10_71_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)91694-1"},{"key":"e_1_2_10_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00089a018"},{"key":"e_1_2_10_73_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00782a078"},{"key":"e_1_2_10_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00082a032"},{"key":"e_1_2_10_75_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja001259k"},{"key":"e_1_2_10_76_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja000531n"},{"key":"e_1_2_10_77_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar4002922"},{"key":"e_1_2_10_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b00242"},{"key":"e_1_2_10_79_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3679736"},{"key":"e_1_2_10_80_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3679749"},{"key":"e_1_2_10_81_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702685"},{"key":"e_1_2_10_81_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201702685"},{"key":"e_1_2_10_82_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.6b04924"},{"key":"e_1_2_10_83_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.70.020101"},{"key":"e_1_2_10_84_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4878944"},{"key":"e_1_2_10_85_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar040198i"},{"key":"e_1_2_10_86_1","doi-asserted-by":"publisher","DOI":"10.1080\/08927022.2014.923574"},{"key":"e_1_2_10_87_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1209316109"},{"key":"e_1_2_10_88_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b00014"},{"key":"e_1_2_10_89_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300511u"},{"key":"e_1_2_10_90_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja802577v"},{"key":"e_1_2_10_91_1","doi-asserted-by":"publisher","DOI":"10.1002\/chin.200542291"},{"key":"e_1_2_10_92_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature05681"},{"key":"e_1_2_10_93_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200900673"},{"key":"e_1_2_10_93_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200900673"},{"key":"e_1_2_10_94_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.201500054"},{"key":"e_1_2_10_95_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2185"},{"key":"e_1_2_10_96_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00337a067"},{"key":"e_1_2_10_97_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00392a047"},{"key":"e_1_2_10_98_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00030a005"},{"key":"e_1_2_10_99_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00127a016"},{"key":"e_1_2_10_100_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4020-2102-2_34"},{"key":"e_1_2_10_101_1","doi-asserted-by":"publisher","DOI":"10.2138\/rmg.2013.75.19"},{"key":"e_1_2_10_102_1","doi-asserted-by":"publisher","DOI":"10.1088\/0953-8984\/14\/44\/504"},{"key":"e_1_2_10_103_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.icarus.2017.03.031"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201705427","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201705427","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201705427","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.201705427","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201705427","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,13]],"date-time":"2023-09-13T22:36:24Z","timestamp":1694644584000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201705427"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,7,24]]},"references-count":112,"journal-issue":{"issue":"37","published-print":{"date-parts":[[2017,9,4]]}},"alternative-id":["10.1002\/anie.201705427"],"URL":"https:\/\/doi.org\/10.1002\/anie.201705427","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,7,24]]}}}