{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T19:44:40Z","timestamp":1791402280717,"version":"4.3.3"},"reference-count":79,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2004,11,18]],"date-time":"2004-11-18T00:00:00Z","timestamp":1100736000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2005,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A synthetic route to enantiomerically pure (1<jats:italic>R<\/jats:italic>,2<jats:italic>S<\/jats:italic>)\u20101\u2010phenylphospholane\u20102\u2010carboxylic acid (<jats:bold>1<\/jats:bold>), which is a phosphorus analogue of proline, has been established. A key step is the deprotonation\u2013carboxylation of the 1\u2010phenylphospholane borane complex <jats:bold>3<\/jats:bold> by using <jats:italic>s<\/jats:italic>BuLi\/1,2\u2010dipiperidinoethane (DPE). Configurational stability of the key intermediate, the amine\u2010coordinated \u03b1\u2010phosphinoalkyllithium borane complex <jats:bold>4<\/jats:bold>, was investigated by employing lithiodestannylation\u2013carboxylation of both diastereomers of the 1\u2010phenyl\u20102\u2010trimethylstannylphospholane borane complex <jats:bold>7<\/jats:bold> in the presence of several kinds of amines, and as a result, <jats:bold>4<\/jats:bold> was found to be configurationally labile even at \u2212100\u2009\u00b0C. The key intermediate, the DPE\u2010coordinated <jats:italic>trans<\/jats:italic>\u20101\u2010phenyl\u20102\u2010phospholanyllithium borane complex <jats:bold>9<\/jats:bold>, was isolated, and the structure was identified by X\u2010ray crystal structure analysis. This is the first X\u2010ray crystal structure determined for an \u03b1\u2010monophosphinoalkyllithium borane complex. Remarkably, the alkyllithium complex is monomeric and tricoordinate at the lithium center with a slightly pyramidalized environment, and the existence of a Li\uf8ffC bond (2.170 \u00c5) has been confirmed. Moreover, <jats:sup>1<\/jats:sup>H\u2013<jats:sup>7<\/jats:sup>Li HOESY and <jats:sup>6<\/jats:sup>Li NMR analyses suggested the structure of <jats:bold>9<\/jats:bold> in solution as well as the existence of an equilibrium between <jats:bold>9<\/jats:bold>, its <jats:italic>cis<\/jats:italic> isomer, and the ion pair <jats:bold>8<\/jats:bold> at room temperature, which was extremely biased towards <jats:bold>9<\/jats:bold> at \u2212100\u2009\u00b0C. Finally, <jats:bold>1<\/jats:bold> was used as a chiral ligand in a palladium\u2010catalyzed allylic substitution, and the desired product was obtained in high yield with good enantioselectivity.<\/jats:p>","DOI":"10.1002\/chem.200400631","type":"journal-article","created":{"date-parts":[[2004,11,18]],"date-time":"2004-11-18T12:20:56Z","timestamp":1100780456000},"page":"361-368","source":"Crossref","is-referenced-by-count":53,"title":["Synthesis of a New Chiral Source, (1<i>R<\/i>,2<i>S<\/i>)\u20101\u2010Phenylphospholane\u20102\u2010carboxylic Acid, via a Key Intermediate \u03b1\u2010Phenylphospholanyllithium Borane Complex: Configurational Stability and X\u2010ray Crystal Structure of an \u03b1\u2010Monophosphinoalkyllithium Borane Complex"],"prefix":"10.1002","volume":"11","author":[{"given":"Xiang\u2010Min","family":"Sun","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kei","family":"Manabe","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"William W.\u2010L.","family":"Lam","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nobuyuki","family":"Shiraishi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jun","family":"Kobayashi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Motoo","family":"Shiro","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hiroaki","family":"Utsumi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shu","family":"Kobayashi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2004,12,15]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-58571-5"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9409804"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020503)114:9<1682::AID-ANGE1682>3.0.CO;2-O"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020503)41:9<1612::AID-ANIE1612>3.0.CO;2-H"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19680802413"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196809422"},{"key":"e_1_2_6_7_2","first-page":"1445","author":"Knowles W. 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These data can be obtained free of charge via www.ccdc.cam.ac.uk\/conts\/retrieving.html (or from the Cambridge Crystallographic Data Centre 12 Union Road Cambridge CB2\u20091EZ UK; fax: (+44)\u20091223\u2010336\u2010033; or deposit@ccdc.cam.ac.uk)."},{"key":"e_1_2_6_47_2","unstructured":"The deboronation of a P\u2010stereogenic phosphine borane complex has been proven to proceed in a stereospecific manner with retention of the configuration.[6c]Furthermore 13C NMR and31P NMR spectra only gave one set of signals indicating that no epimerization occurred during the deboronation."},{"key":"e_1_2_6_48_2","unstructured":"\u00a0"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)83618-9"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00745a034"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00534a025"},{"key":"e_1_2_6_52_2","unstructured":"The low yields in the reactions using DPE are probably due to the low solubility of the DPE complex ofsBuLi at \u2212100\u2009\u00b0C."},{"key":"e_1_2_6_53_2","unstructured":"X\u2010ray crystal structure analysis of6: A crystal of6was obtained from an Et2O\u2013hexane solution: formula C22H39BLiN2P formula weight 380.29 crystal dimensions 0.35\u00d70.10\u00d70.07 mm monoclinic space groupC2\/c a=29.81(1) b=9.235(3) c=20.445(7) \u00c5 \u03b2=125.76(3)\u00b0 V=4567(2) \u00c53 Z=8 \u03c1calcd=1.106 g\u2009cm\u22123 \u03bc=1.29 cm\u22121 2\u03b8max=60.1o; 27\u2009124 reflections measured 6634 unique reflections;R1=0.057 Rw=0.119. Rigaku RAXIS\u2010RAPID Imaging Plate diffractometer (93 K radiation\u03bb(MoK\u03b1)=0.71075 \u00c5). The structure was solved by direct methods (SHELXS\u201086).[12]"},{"key":"e_1_2_6_54_2","unstructured":"\u00a0"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00808a057"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39870000630"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19961290414"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200351308"},{"key":"e_1_2_6_58_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200351308"},{"key":"e_1_2_6_59_2","unstructured":"\u00a0"},{"key":"e_1_2_6_60_2","unstructured":"The NMR spectra of9were consistent with those of the deprotonated3in the presence of DPE in [D10]Et2O."},{"key":"e_1_2_6_61_2","unstructured":"Low\u2010temperature1H 13C and31P NMR analyses did not give useful information to discuss here."},{"key":"e_1_2_6_62_2","unstructured":"\u00a0"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00055a035"},{"key":"e_1_2_6_64_2","unstructured":"We assume that these two peaks constitute a doublet because the coupling constant (2.3 Hz) is within a typical range of2J(6Li 31P)=5 Hz. A broad singlet was observed in31P NMR spectrum at \u2212100\u2009\u00b0C because the phosphorus not only coupled with6Li but also coupled with B."},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00205a030"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00062a010"},{"key":"e_1_2_6_67_2","unstructured":"The chemical shift of8was deduced from the6Li NMR spectrum of DPE\u2010coordinated lithium tetrakis(pentafluorophenyl)borate in [D10]Et2O at room temperature. A signal appeared at higher field (\u03b4=0.53 ppm) than the time\u2010averaged signal of6Li\u20109(\u03b4=0.81 ppm). We could not distinguish the NMR signals of thecisisomer4\u2009b."},{"key":"e_1_2_6_68_2","unstructured":"Use oftBu\u2010 instead of Ph\u2010substituted phospholanes resulted in high selectivity."},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270100004066"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390220"},{"key":"e_1_2_6_70_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390251"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol034299c"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200400631","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200400631","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:18:58Z","timestamp":1760296738000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200400631"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2004,12,15]]},"references-count":79,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2005,1]]}},"alternative-id":["10.1002\/chem.200400631"],"URL":"https:\/\/doi.org\/10.1002\/chem.200400631","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2004,12,15]]}}}