{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T14:42:40Z","timestamp":1787496160331,"version":"build-2736575974"},"reference-count":116,"publisher":"Wiley","issue":"68","license":[{"start":{"date-parts":[[2021,8,4]],"date-time":"2021-08-04T00:00:00Z","timestamp":1628035200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004189","name":"Max-Planck-Gesellschaft","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004189","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2021,12,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Alkynyl\u2010B(aam) (aam=anthranilamidato) derivatives are readily available bench\u2010stable compounds that undergo remarkably selective reactions with Bu\n                    <jats:sub>3<\/jats:sub>\n                    SnH in the presence of [Cp*RuCl]\n                    <jats:sub>4<\/jats:sub>\n                    as the catalyst. The addition follows a stereochemically unorthodox\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010selective course; in terms of regioselectivity, the Bu\n                    <jats:sub>3<\/jats:sub>\n                    Sn\u2010 unit is delivered with high fidelity to the C\u2010atom of the triple bond adjacent to the boracyclic head group (\u201c\n                    <jats:italic>alpha,trans<\/jats:italic>\n                    \u2010addition\u201d). This outcome is deemed to reflect a hydrogen bonding interaction between the protic \u2212NH groups of the benzo\u20101,3,2\u2010diazaborininone ring system and the polarized [Ru\u2212Cl] bond in the loaded catalyst, which locks the substrate in place in a favorable orientation relative to the incoming reagent. The resulting isomerically (almost) pure\n                    <jats:italic>gem<\/jats:italic>\n                    \u2010dimetalated building blocks are amenable to numerous downstream functionalizations; most remarkable is the ability to subject the \u2212B(aam) moiety to Suzuki\u2010Miyaura cross coupling without need for prior hydrolysis while keeping the adjacent Bu\n                    <jats:sub>3<\/jats:sub>\n                    Sn\u2010 group intact. Alternatively, the tin residue can be engaged in selective tin\/halogen exchange without touching the boron substituent; the fact that the two \u2010NH entities of \u2212B(aam) do not protonate organozinc reagents and hence do not interfere with Negishi reactions of the alkenyl halides thus formed is another virtue of this so far underutilized boracycle. Overall, the ruthenium catalyzed\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010hydrostannation of alkynyl\u2010B(aam) derivatives opens a practical gateway to isomerically pure trisubstituted alkenes of many different substitution patterns by sequential functionalization of the 1\u2010alkenyl\u20101,1\u2010heterobimetallic adducts primarily formed.\n                  <\/jats:p>","DOI":"10.1002\/chem.202101901","type":"journal-article","created":{"date-parts":[[2021,7,9]],"date-time":"2021-07-09T07:18:20Z","timestamp":1625815100000},"page":"17002-17011","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Regioselective\n                    <i>trans<\/i>\n                    \u2010Hydrostannation of Boron\u2010Capped Alkynes"],"prefix":"10.1002","volume":"27","author":[{"given":"Romain","family":"Melot","sequence":"first","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim an der RuhrM\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tomas J.","family":"Saiegh","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim an der RuhrM\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0098-3417","authenticated-orcid":false,"given":"Alois","family":"F\u00fcrstner","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim an der RuhrM\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,8,4]]},"reference":[{"key":"e_1_2_6_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b09782"},{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0121033"},{"key":"e_1_2_6_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja026457l"},{"key":"e_1_2_6_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0528580"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/B207169J"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.05.042"},{"key":"e_1_2_6_7_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-2005-861874"},{"key":"e_1_2_6_8_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.20150317"},{"key":"e_1_2_6_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201205946"},{"key":"e_1_2_6_10_1","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201506075"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b00665"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411618"},{"key":"e_1_2_6_14_1","unstructured":"\u00a0"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904255"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904256"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201912161"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c07808"},{"key":"e_1_2_6_19_1","unstructured":"\u00a0"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202007030"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202101176"},{"key":"e_1_2_6_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201307584"},{"key":"e_1_2_6_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201902228"},{"key":"e_1_2_6_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/b703397d"},{"key":"e_1_2_6_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b01475"},{"key":"e_1_2_6_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201311080"},{"key":"e_1_2_6_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b12517"},{"key":"e_1_2_6_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c08582"},{"key":"e_1_2_6_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja034833b"},{"key":"e_1_2_6_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja405752w"},{"key":"e_1_2_6_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b09658"},{"key":"e_1_2_6_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b03214"},{"key":"e_1_2_6_33_1","unstructured":"With the exeption oftrans-hydrogenation which obviously causes no regioselectivity problem."},{"key":"e_1_2_6_34_1","unstructured":"The regiochemical course oftrans-hydroboration cannot be controlled in this way since (pin)BH reacts with the -OH group of a propargyl alcohol. In many cases however high levels of regioselectivity can be reached by proper choice of the O-protecting group see Ref.\u2005[14]."},{"key":"e_1_2_6_35_1","unstructured":"\u00a0"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201501608"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b01431"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701391"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201705550"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201801344"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.7b02871"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201812096"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b12185"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202015243"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016475"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016477"},{"key":"e_1_2_6_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr990288e"},{"key":"e_1_2_6_48_1","unstructured":"For pioneering studies into 1 1-heterobimetallic alkenes for organic synthesis see the following and literature cited therein:"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(92)80007-7"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00101a061"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja077664u"},{"key":"e_1_2_6_52_1","unstructured":"For cursory reports on highly sensitive 1 1-borio-stannioalkene derivatives of little preaprative utility see:"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)92022-9"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199163030403"},{"key":"e_1_2_6_55_1","unstructured":"More electron rich triple bonds bind more tightly to the ruthenium catalyst; this higher affinity favors upload of two alkynes onto the [Cp*RuCl] fragment which is unfavorable or even detrimental in the present context; note that productive hydroelementation mandates formation of a loaded catalyst carrying one alkyne as well as one R3E\u2212H unit; see Ref.\u2005[16 18 19]."},{"key":"e_1_2_6_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c05334"},{"key":"e_1_2_6_57_1","unstructured":"\u00a0"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01065a639"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200304793"},{"key":"e_1_2_6_60_1","unstructured":"\u00a0"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja067975p"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol702420x"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol9003096"},{"key":"e_1_2_6_64_1","unstructured":"\u00a0"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b03666"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b03667"},{"key":"e_1_2_6_67_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202001460"},{"key":"e_1_2_6_68_1","unstructured":"\u00a0"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.0c01901"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol502285s"},{"key":"e_1_2_6_71_1","unstructured":"The deshielding of the -OH proton oftert-propargyl alcohol upon binding of the triple bond to [Cp*RuCl] is on the order of 3.2\u2005ppm see Ref.\u2005[18]."},{"key":"e_1_2_6_72_1","unstructured":"\u00a0"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01532a053"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01473a025"},{"key":"e_1_2_6_75_1","unstructured":"\u00a0"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol200764g"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2011.916"},{"key":"e_1_2_6_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.7b00747"},{"key":"e_1_2_6_79_1","unstructured":"\u00a0"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC02002K"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC10252J"},{"key":"e_1_2_6_82_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201900827"},{"key":"e_1_2_6_83_1","unstructured":"For instance we are unaware of any alkynyl-B(aam) derivative described in the literature."},{"key":"e_1_2_6_84_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201700342"},{"key":"e_1_2_6_85_1","doi-asserted-by":"publisher","DOI":"10.2174\/138527207781662519"},{"key":"e_1_2_6_86_1","unstructured":"In the propargyl alcohol series it was shown that an emerging hydrogen bond also favors the upload of the substrate onto the catalyst and therefore also leads to increased reactivity."},{"key":"e_1_2_6_87_1","unstructured":"In the propargyl alcohol series this cationic ruthenium complex leads to much lower regioselectivites than the chloride-containing comply [Cp*RuCl]4 see Ref.\u2005[16]."},{"key":"e_1_2_6_88_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b00182"},{"key":"e_1_2_6_89_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85245-6"},{"key":"e_1_2_6_90_1","doi-asserted-by":"publisher","DOI":"10.1080\/00397911.2012.751612"},{"key":"e_1_2_6_91_1","unstructured":"Poor stability of the boronate ester initially formed seems to be responsible for the low yield of product4and20 whereas solubility issues at the stage of the lithium acetylide are the culprit in case of compound18."},{"key":"e_1_2_6_92_1","unstructured":"Deposition Numbers2083795 (22) 2083794 (47\u2009d)contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_6_93_1","first-page":"202","volume":"49","author":"Schaubach S.","year":"2017","journal-title":"Synthesis"},{"key":"e_1_2_6_94_1","volume-title":"Metal-Catalyzed Cross-Coupling Reactions"},{"key":"e_1_2_6_95_1","unstructured":"\u00a0"},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00448"},{"key":"e_1_2_6_97_2","first-page":"1","volume-title":"Organic Reactions","author":"Farina V.","year":"2004"},{"key":"e_1_2_6_98_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00141a010"},{"key":"e_1_2_6_99_1","doi-asserted-by":"publisher","DOI":"10.1039\/b805299a"},{"key":"e_1_2_6_100_1","unstructured":"\u00a0"},{"key":"e_1_2_6_101_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c12948"},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202011472"},{"key":"e_1_2_6_103_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b05094"},{"key":"e_1_2_6_104_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201100178"},{"key":"e_1_2_6_105_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201005850"},{"key":"e_1_2_6_106_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja072334v"},{"key":"e_1_2_6_107_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200704024"},{"key":"e_1_2_6_108_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201702470"},{"key":"e_1_2_6_109_1","unstructured":"The organocopper intermediate is more likely responsible for this isomerization; if it were the organopalladium compound formed after transmetalation the Negishi reactions shown in Scheme\u20057 should also be plaqued by isomerization as they proceed through a similar organopalladium intermediate."},{"key":"e_1_2_6_110_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c01700"},{"key":"e_1_2_6_111_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-1982-29712"},{"key":"e_1_2_6_112_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201605444"},{"key":"e_1_2_6_113_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201100420"},{"key":"e_1_2_6_114_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.80.233"},{"key":"e_1_2_6_115_1","doi-asserted-by":"publisher","DOI":"10.1002\/1615-4169(20010430)343:4<343::AID-ADSC343>3.0.CO;2-Z"},{"key":"e_1_2_6_116_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020022z"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202101901","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202101901","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202101901","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:46:32Z","timestamp":1760301992000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202101901"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,8,4]]},"references-count":116,"journal-issue":{"issue":"68","published-print":{"date-parts":[[2021,12,6]]}},"alternative-id":["10.1002\/chem.202101901"],"URL":"https:\/\/doi.org\/10.1002\/chem.202101901","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,8,4]]},"assertion":[{"value":"2021-05-31","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2021-08-04","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}