{"id":"https://openalex.org/W4253000545","doi":"https://doi.org/10.26434/chemrxiv.13317902","title":"A Theoretical Stereoselectivity Model of Photochemical Denitrogenations of Diazoalkanes Towards Strained 1,3-Dihalogenated Bicyclobutanes","display_name":"A Theoretical Stereoselectivity Model of Photochemical Denitrogenations of Diazoalkanes Towards Strained 1,3-Dihalogenated Bicyclobutanes","publication_year":2020,"publication_date":"2020-12-03","ids":{"openalex":"https://openalex.org/W4253000545","doi":"https://doi.org/10.26434/chemrxiv.13317902"},"language":"en","primary_location":{"id":"doi:10.26434/chemrxiv.13317902","doi":"https://doi.org/10.26434/chemrxiv.13317902","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.13317902","pdf_url":null,"source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by-nc-nd","license_id":"https://openalex.org/licenses/cc-by-nc-nd","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"volume":null,"type":"preprint","indexed_in":["crossref"],"open_access":{"is_oa":true,"oa_status":"green","oa_url":"https://doi.org/10.26434/chemrxiv.13317902","any_repository_has_fulltext":true},"authorships":[{"author_position":"first","author":{"id":"https://openalex.org/A5082039348","display_name":"Jingbai Li","orcid":"https://orcid.org/0000-0003-4743-0318","observed_orcids":["https://orcid.org/0000-0003-4743-0318"]},"institutions":[{"id":"https://openalex.org/I12912129","display_name":"Northeastern University","ror":"https://ror.org/04t5xt781","country_code":"US","type":"education","lineage":["https://openalex.org/I12912129"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"Jingbai Li","raw_affiliation_strings":["Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115"],"raw_orcid":"https://orcid.org/0000-0003-4743-0318","affiliations":[{"raw_affiliation_string":"Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115","institution_ids":["https://openalex.org/I12912129"]}]},{"author_position":"middle","author":{"id":null,"display_name":"Rachel Stein","orcid":null,"observed_orcids":[]},"institutions":[{"id":"https://openalex.org/I12912129","display_name":"Northeastern University","ror":"https://ror.org/04t5xt781","country_code":"US","type":"education","lineage":["https://openalex.org/I12912129"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"Rachel Stein","raw_affiliation_strings":["Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115","institution_ids":["https://openalex.org/I12912129"]}]},{"author_position":"last","author":{"id":null,"display_name":"Steven Lopez","orcid":null,"observed_orcids":[]},"institutions":[{"id":"https://openalex.org/I12912129","display_name":"Northeastern University","ror":"https://ror.org/04t5xt781","country_code":"US","type":"education","lineage":["https://openalex.org/I12912129"]}],"countries":["US"],"is_corresponding":false,"raw_author_name":"Steven Lopez","raw_affiliation_strings":["Northeastern University"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Northeastern University","institution_ids":["https://openalex.org/I12912129"]}]}],"institutions":[],"countries_distinct_count":1,"institutions_distinct_count":1,"corresponding_author_ids":[],"corresponding_institution_ids":["https://openalex.org/I12912129"],"apc_list":null,"apc_paid":null,"fwci":null,"has_fulltext":false,"cited_by_count":0,"citation_normalized_percentile":null,"cited_by_percentile_year":null,"biblio":{"volume":null,"issue":null,"first_page":null,"last_page":null},"is_retracted":false,"is_paratext":false,"is_xpac":false,"primary_topic":{"id":"https://openalex.org/T13253","display_name":"Chemical Reactions and Mechanisms","score":0.9648000001907349,"subfield":{"id":"https://openalex.org/subfields/1606","display_name":"Physical and Theoretical Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},"topics":[{"id":"https://openalex.org/T13253","display_name":"Chemical Reactions and Mechanisms","score":0.9648000001907349,"subfield":{"id":"https://openalex.org/subfields/1606","display_name":"Physical and Theoretical Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T12893","display_name":"Organic Chemistry Cycloaddition Reactions","score":0.008500000461935997,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T11611","display_name":"Cyclopropane Reaction Mechanisms","score":0.007899999618530273,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}}],"keywords":[{"id":"https://openalex.org/keywords/diazoalkanes","display_name":"diazoalkanes","score":0.9610000252723694},{"id":"https://openalex.org/keywords/stereoselectivity","display_name":"stereoselectivity","score":0.9240000247955322},{"id":"https://openalex.org/keywords/double-inversion","display_name":"double inversion","score":0.5559999942779541},{"id":"https://openalex.org/keywords/n2-extrusion","display_name":"N2 extrusion","score":0.722000002861023},{"id":"https://openalex.org/keywords/diastereomeric-excess","display_name":"diastereomeric excess","score":0.7590000033378601},{"id":"https://openalex.org/keywords/hyperconjugation","display_name":"hyperconjugation","score":0.6679999828338623},{"id":"https://openalex.org/keywords/potential-energy-surface","display_name":"potential energy surface","score":0.7139999866485596},{"id":"https://openalex.org/keywords/nonadiabatic-dynamics","display_name":"nonadiabatic dynamics","score":0.796999990940094},{"id":"https://openalex.org/keywords/casscf-caspt2","display_name":"CASSCF/CASPT2","score":0.7450000047683716}],"concepts":[{"id":"https://openalex.org/C185592680","wikidata":"https://www.wikidata.org/wiki/Q2329","display_name":"Chemistry","level":0,"score":0.8576284646987915},{"id":"https://openalex.org/C181647583","wikidata":"https://www.wikidata.org/wiki/Q903429","display_name":"Stereoselectivity","level":3,"score":0.8291294574737549},{"id":"https://openalex.org/C41455181","wikidata":"https://www.wikidata.org/wiki/Q1062109","display_name":"Complete active space","level":4,"score":0.6151176691055298},{"id":"https://openalex.org/C65956243","wikidata":"https://www.wikidata.org/wiki/Q2664086","display_name":"Basis set","level":3,"score":0.5931161642074585},{"id":"https://openalex.org/C24961977","wikidata":"https://www.wikidata.org/wiki/Q225972","display_name":"Bicyclic molecule","level":2,"score":0.5758160352706909},{"id":"https://openalex.org/C125277925","wikidata":"https://www.wikidata.org/wiki/Q2572687","display_name":"Potential energy surface","level":3,"score":0.49345579743385315},{"id":"https://openalex.org/C147597530","wikidata":"https://www.wikidata.org/wiki/Q369472","display_name":"Computational chemistry","level":1,"score":0.47820544242858887},{"id":"https://openalex.org/C68381374","wikidata":"https://www.wikidata.org/wiki/Q258652","display_name":"Double bond","level":2,"score":0.4732830226421356},{"id":"https://openalex.org/C71240020","wikidata":"https://www.wikidata.org/wiki/Q186011","display_name":"Stereochemistry","level":1,"score":0.4540071189403534},{"id":"https://openalex.org/C32909587","wikidata":"https://www.wikidata.org/wiki/Q11369","display_name":"Molecule","level":2,"score":0.24525323510169983},{"id":"https://openalex.org/C178790620","wikidata":"https://www.wikidata.org/wiki/Q11351","display_name":"Organic chemistry","level":1,"score":0.14382430911064148},{"id":"https://openalex.org/C152365726","wikidata":"https://www.wikidata.org/wiki/Q1048589","display_name":"Density functional theory","level":2,"score":0.1123540997505188},{"id":"https://openalex.org/C161790260","wikidata":"https://www.wikidata.org/wiki/Q82264","display_name":"Catalysis","level":2,"score":0.07455244660377502}],"mesh":[],"locations_count":1,"locations":[{"id":"doi:10.26434/chemrxiv.13317902","doi":"https://doi.org/10.26434/chemrxiv.13317902","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.13317902","pdf_url":null,"source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by-nc-nd","license_id":"https://openalex.org/licenses/cc-by-nc-nd","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"}],"best_oa_location":{"id":"doi:10.26434/chemrxiv.13317902","doi":"https://doi.org/10.26434/chemrxiv.13317902","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.13317902","pdf_url":null,"source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by-nc-nd","license_id":"https://openalex.org/licenses/cc-by-nc-nd","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"sustainable_development_goals":[],"sustainable_development_goals_aurora":[{"display_name":"Affordable and clean energy","score":0.8399999737739563,"id":"https://metadata.un.org/sdg/7"}],"study_designs":[],"awards":[{"id":"https://openalex.org/G1086542226","display_name":"Collaborative Research: Accelerating the Discovery of Electronic Materials through Human-Computer Active Search","funder_award_id":"1940307","funder_id":"https://openalex.org/F4320306076","funder_display_name":"National Science Foundation"},{"id":"https://openalex.org/G4132190082","display_name":null,"funder_award_id":"N00014-12-1-0828","funder_id":"https://openalex.org/F4320337345","funder_display_name":"Office of Naval Research"},{"id":"https://openalex.org/G7685818843","display_name":null,"funder_award_id":"N00014-12-1","funder_id":"https://openalex.org/F4320337345","funder_display_name":"Office of Naval Research"},{"id":"https://openalex.org/G8876996369","display_name":null,"funder_award_id":"N00014","funder_id":"https://openalex.org/F4320337345","funder_display_name":"Office of Naval Research"}],"funders":[{"id":"https://openalex.org/F4320306076","display_name":"National Science Foundation","ror":"https://ror.org/021nxhr62"},{"id":"https://openalex.org/F4320337345","display_name":"Office of Naval Research","ror":"https://ror.org/00rk2pe57"}],"has_content":{"grobid_xml":false,"pdf":false},"content_urls":null,"referenced_works_count":35,"referenced_works":["https://openalex.org/W1981368803","https://openalex.org/W1986525348","https://openalex.org/W1991093311","https://openalex.org/W2011428114","https://openalex.org/W2027703345","https://openalex.org/W2029876016","https://openalex.org/W2038767330","https://openalex.org/W2043030248","https://openalex.org/W2044106590","https://openalex.org/W2045952721","https://openalex.org/W2051004637","https://openalex.org/W2055032509","https://openalex.org/W2066556212","https://openalex.org/W2068920655","https://openalex.org/W2069006374","https://openalex.org/W2077323050","https://openalex.org/W2077949729","https://openalex.org/W2079676480","https://openalex.org/W2091149553","https://openalex.org/W2138305674","https://openalex.org/W2332455789","https://openalex.org/W2594550352","https://openalex.org/W2796309353","https://openalex.org/W2951782452","https://openalex.org/W2951857627","https://openalex.org/W2952843404","https://openalex.org/W2953024690","https://openalex.org/W2972738436","https://openalex.org/W2995791123","https://openalex.org/W3005134582","https://openalex.org/W3005314700","https://openalex.org/W3092103731","https://openalex.org/W4250981941","https://openalex.org/W4251375550","https://openalex.org/W4253257881"],"related_works":["https://openalex.org/W3128140286","https://openalex.org/W4414901612","https://openalex.org/W2044106590","https://openalex.org/W2470176954","https://openalex.org/W2014642519","https://openalex.org/W2003245920","https://openalex.org/W1987631103","https://openalex.org/W2066428466","https://openalex.org/W2594550352","https://openalex.org/W2079455029"],"abstract_inverted_index":{"Photochemical":[0],"reactions":[1,31],"exemplify":[2],"\u2018green\u2019":[3],"chemistry":[4],"and":[5,35,51,67,83,100,132,143,178,184],"are":[6],"essential":[7],"for":[8,41,88,123,181,192,232],"synthesizing":[9],"highly":[10],"strained":[11],"molecules":[12],"with":[13,16,32,62,76,175],"mild":[14],"conditions":[15],"light.":[17],"The":[18,78,136,146,161,214],"light-promoted":[19],"denitrogenation":[20],"of":[21,44,118,190,210],"bicyclic":[22],"azoalkanes":[23],"affords":[24],"functionalized,":[25],"stereoenriched":[26],"bicyclo[1.1.0]butanes.":[27],"We":[28,53,127],"revisited":[29],"these":[30],"multireference":[33],"calculations":[34,61,94],"non-adiabatic":[36],"molecular":[37],"dynamics":[38],"(NAMD)":[39],"simulations":[40,174],"a":[42,103,225],"series":[43],"diazabicyclo[2.1.1]hexenes":[45],"to":[46,102,158,224],"predict":[47],"the":[48,71,89,110,193,200,206,230],"photophysics,":[49],"reactivities,":[50],"stereoselectivities.":[52],"used":[54],"complete":[55,130],"active":[56,65],"space":[57,66],"self-consistent":[58],"field":[59],"(CASSCF)":[60],"an":[63],"(8,8)":[64],"ANO-S-VDZP":[68],"basis":[69],"set;":[70],"CASSCF":[72],"energies":[73],"were":[74],"corrected":[75],"CASPT2(8,8)/ANO-S-VDZP.":[77],"excitation":[79],"is":[80],"consistently":[81],"n\u2192\u03c0*":[82],"ranges":[84],"from":[85],"3.77\u20133.91":[86],"eV":[87],"diazabicyclo[2.1.1]hexenes.":[90],"Minimum":[91],"energy":[92,105,202],"path":[93],"showed":[95],"stepwise":[96],"C\u2013N":[97],"bond":[98],"breaking":[99],"led":[101],"minimum":[104],"crossing":[106],"point,":[107],"which":[108],"favors":[109],"stereochemical":[111,133,147],"\u2018double":[112],"inversion\u2019":[113],"bicyclobutane":[114,141,155],"product.":[115],"Wigner":[116],"sampling":[117],"1":[119],"provided":[120],"Franck-Condon":[121],"points":[122],"692":[124],"NAMD":[125,173],"trajectories.":[126],"identified":[128],"competing":[129],"stereoselective":[131,137],"scrambling":[134,148],"pathways.":[135],"pathways":[138,149],"feature":[139],"concerted":[140],"inversion":[142,195],"N2":[144,151],"extrusion.":[145],"involve":[150],"extrusion":[152],"followed":[153],"by":[154],"planarization,":[156],"leading":[157],"non-stereoselective":[159],"outcomes.":[160],"predicted":[162,186],"diastereomeric":[163,187],"excess":[164,188],"almost":[165],"exactly":[166],"match":[167],"experiment":[168],"(calc.d.e.=46%":[169],"vs.":[170],"exp.d.e.=47%).":[171],"Our":[172],"672,":[176],"568,":[177],"596":[179],"trajectories":[180],"1-F,":[182],"1-Cl,":[183],"1-Br":[185],"(d.e.)":[189],"94\u201397%":[191],"double":[194,233],"products.":[196],"Halogenation":[197],"significantly":[198],"perturbs":[199],"potential":[201],"surface":[203],"(PES)":[204],"towards":[205],"retention":[207],"products":[208],"because":[209],"powerful":[211],"hyperconjugative":[212,221],"interactions.":[213],"nC\u2192\u03c3*C\u2013X,":[215],"X":[216],"=":[217],"F,":[218],"Cl,":[219],"Br":[220],"interaction":[222],"leads":[223],"broadened":[226],"shoulder":[227],"region":[228],"on":[229],"PES":[231],"inversion.":[234]},"counts_by_year":[],"updated_date":"2026-10-12T09:40:04.860316","created_date":"2022-05-12T00:00:00"}
