{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,27]],"date-time":"2026-01-27T21:54:17Z","timestamp":1769550857076,"version":"3.49.0"},"reference-count":58,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2008,3,25]],"date-time":"2008-03-25T00:00:00Z","timestamp":1206403200000},"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":[[2008,5,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>(1<jats:italic>R<\/jats:italic>)\u20101,3\u2010Benzazaphospholes <jats:bold>1\u2009a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>, P\uf8feCH\u2010NR heterocycles of the indole type, react with <jats:italic>t<\/jats:italic>BuLi in two ways, depending on the steric demand of the <jats:italic>N<\/jats:italic>\u2010substituent and the polarity of the medium. The presence of small <jats:italic>N<\/jats:italic>\u2010alkyl groups induces CH\u2010deprotonation in the 2\u2010position to give hetaryllithium reagents <jats:bold>2\u2009a<\/jats:bold> and <jats:bold>2\u2009b<\/jats:bold>, whereas bulky <jats:italic>N<\/jats:italic>\u2010substituents and nonpolar solvents change the reactivity towards addition at the P\uf8feC bond. The preferred regioselectivity is <jats:italic>tert<\/jats:italic>\u2010butylation at phosphorus, occurring with excellent diastereoselectivity for <jats:italic>trans<\/jats:italic>\u2010adducts <jats:bold>3\u2009b<\/jats:bold> and <jats:bold>3\u2009c<\/jats:bold>, but the inverse <jats:italic>tert<\/jats:italic>\u2010butylation at C2 to <jats:bold>5\u2009b<\/jats:bold> was also observed. <jats:italic>N<\/jats:italic>\u2010Neopentyl groups, with intermediate steric demand, give rise to formation of mixtures in ethers but allow switching either to selective CH lithiation in THF\/KO<jats:italic>t<\/jats:italic>Bu or to addition in pentane. Bulkier <jats:italic>N<\/jats:italic>\u2010adamantyl groups always cause preferred addition. Protonation, silylation, and carboxylation were used to convert the P\uf8feCLi\u2010NR, (<jats:italic>E<\/jats:italic>)\u2010<jats:italic>t<\/jats:italic>BuP\u2010CHLi\u2010NR, and LiP\u2010CH(<jats:italic>t<\/jats:italic>Bu)\u2010NR species into the corresponding \u03c3<jats:sup>2<\/jats:sup>\u2010P or \u03c3<jats:sup>3<\/jats:sup>\u2010P compounds <jats:bold>4\u2009b<\/jats:bold> and <jats:bold>6\u2009a<\/jats:bold>,<jats:bold>b<\/jats:bold>, <jats:bold>7\u2009b<\/jats:bold>,<jats:bold>c<\/jats:bold>, or <jats:bold>8\u2009b<\/jats:bold>\u2013<jats:bold>10\u2009b<\/jats:bold> with additional N and\/or O donor sites. Slow diffusion\u2010controlled air oxidation of <jats:bold>10\u2009b<\/jats:bold> led to the <jats:italic>meso<\/jats:italic>\u2010diphosphine <jats:bold>11\u2009b<\/jats:bold>. Preferred \u03b7<jats:sup>1<\/jats:sup>\u2010P coordination was shown for an [Rh(cod)Cl] complex <jats:bold>12\u2009b<\/jats:bold>, and the potential of the new ligands <jats:bold>4\u2009b<\/jats:bold> and <jats:bold>7\u2009b<\/jats:bold> in catalysis was demonstrated by examples of Pd\u2010catalyzed C\uf8ffN coupling and Ni\u2010catalyzed ethylene oligomerization (TON&gt;6300). Crystal structures of <jats:bold>6\u2009b<\/jats:bold>, <jats:bold>11\u2009b<\/jats:bold>, and <jats:bold>12\u2009b<\/jats:bold> are presented.<\/jats:p>","DOI":"10.1002\/chem.200702016","type":"journal-article","created":{"date-parts":[[2008,3,25]],"date-time":"2008-03-25T11:46:38Z","timestamp":1206445598000},"page":"4328-4335","source":"Crossref","is-referenced-by-count":39,"title":["Sterically and Polarity\u2010Controlled Reactions of <i>t<\/i>BuLi with P\uf8feCH\u2010NR Heterocycles: Novel Heterocyclic P\u2010 and P,O\u2010Ligands and Preliminary Tests in Transition\u2010Metal Catalysis"],"prefix":"10.1002","volume":"14","author":[{"given":"Bhaskar\u2005R.","family":"Aluri","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Markus\u2005K.","family":"Kindermann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter\u2005G.","family":"Jones","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Joachim","family":"Heinicke","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,4,29]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For example"},{"key":"e_1_2_6_2_2","doi-asserted-by":"crossref","first-page":"253","DOI":"10.1016\/B0-08-043748-6\/01049-5","volume-title":"Comprehensive Coordination Chemistry\u2005II, Vol.\u20051","author":"Downing J. 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