{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T17:50:47Z","timestamp":1760550647162,"version":"3.40.5"},"reference-count":50,"publisher":"Beilstein Institut","license":[{"start":{"date-parts":[[2018,9,7]],"date-time":"2018-09-07T00:00:00Z","timestamp":1536278400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2018,9,7]],"date-time":"2018-09-07T00:00:00Z","timestamp":1536278400000},"content-version":"am","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2018,9,7]],"date-time":"2018-09-07T00:00:00Z","timestamp":1536278400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Beilstein J. Org. Chem."],"accepted":{"date-parts":[[2018,8,24]]},"abstract":"<jats:p>Two routes to the title compounds are evaluated. First, a ca. 0.01 M CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> solution of H<jats:sub>3<\/jats:sub>B\u00b7P((CH<jats:sub>2<\/jats:sub>)<jats:sub>6<\/jats:sub>CH=CH<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub> (<jats:bold>1<\/jats:bold>\u00b7BH<jats:sub>3<\/jats:sub>) is treated with 5 mol % of Grubbs' first generation catalyst (0 \u00b0C to reflux), followed by H<jats:sub>2<\/jats:sub> (5 bar) and Wilkinson's catalyst (55 \u00b0C). Column chromatography affords H<jats:sub>3<\/jats:sub>B\u00b7P(<jats:italic>n-<\/jats:italic>C<jats:sub>8<\/jats:sub>H<jats:sub>17<\/jats:sub>)<jats:sub>3<\/jats:sub> (1%), H<jats:sub>3<\/jats:sub>B\u00b7<jats:italic><jats:underline>P<\/jats:underline><\/jats:italic>((CH<jats:sub>2<\/jats:sub>)<jats:sub>13<\/jats:sub><jats:italic><jats:underline>C<\/jats:underline><\/jats:italic>H<jats:sub>2<\/jats:sub>)(<jats:italic>n<\/jats:italic>-C<jats:sub>8<\/jats:sub>H<jats:sub>17<\/jats:sub>) (8%; see text for tie bars that indicate additional phosphorus\u2013carbon linkages, which are coded in the abstract with italics), H<jats:sub>3<\/jats:sub>B\u00b7<jats:italic><jats:underline>P<\/jats:underline><\/jats:italic>((CH<jats:sub>2<\/jats:sub>)<jats:sub>13<\/jats:sub><jats:italic><jats:underline>C<\/jats:underline><\/jats:italic>H<jats:sub>2<\/jats:sub>)((CH<jats:sub>2<\/jats:sub>)<jats:sub>14<\/jats:sub>)<jats:italic><jats:underline>P<\/jats:underline><\/jats:italic>((CH<jats:sub>2<\/jats:sub>)<jats:sub>13<\/jats:sub><jats:italic><jats:underline>C<\/jats:underline><\/jats:italic>H<jats:sub>2<\/jats:sub>)\u00b7BH<jats:sub>3<\/jats:sub> (<jats:bold>6<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub>, 10%), <jats:italic>in,out<\/jats:italic>-H<jats:sub>3<\/jats:sub>B\u00b7P((CH<jats:sub>2<\/jats:sub>)<jats:sub>14<\/jats:sub>)<jats:sub>3<\/jats:sub>P\u00b7BH<jats:sub>3<\/jats:sub> (<jats:italic>in,out<\/jats:italic>-<jats:bold>2<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub>, 4%) and the stereoisomer (<jats:italic>in,in<\/jats:italic>\/<jats:italic>out,out<\/jats:italic>)-<jats:bold>2<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (2%). Four of these structures are verified by independent syntheses. Second, 1,14-tetradecanedioic acid is converted (reduction, bromination, Arbuzov reaction, LiAlH<jats:sub>4<\/jats:sub>) to H<jats:sub>2<\/jats:sub>P((CH<jats:sub>2<\/jats:sub>)<jats:sub>14<\/jats:sub>)PH<jats:sub>2<\/jats:sub> (<jats:bold>10<\/jats:bold>; 76% overall yield). The reaction with H<jats:sub>3<\/jats:sub>B\u00b7SMe<jats:sub>2<\/jats:sub> gives <jats:bold>10<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub>, which is treated with <jats:italic>n<\/jats:italic>-BuLi (4.4 equiv) and Br(CH<jats:sub>2<\/jats:sub>)<jats:sub>6<\/jats:sub>CH=CH<jats:sub>2<\/jats:sub> (4.0 equiv) to afford the tetraalkenyl precursor (H<jats:sub>2<\/jats:sub>C=CH(CH<jats:sub>2<\/jats:sub>)<jats:sub>6<\/jats:sub>)<jats:sub>2<\/jats:sub>(H<jats:sub>3<\/jats:sub>B)P((CH<jats:sub>2<\/jats:sub>)<jats:sub>14<\/jats:sub>)P(BH<jats:sub>3<\/jats:sub>)((CH<jats:sub>2<\/jats:sub>)<jats:sub>6<\/jats:sub>CH=CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>11<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub>; 18%). Alternative approaches to <jats:bold>11<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (e.g., via <jats:bold>11<\/jats:bold>) were unsuccessful. An analogous metathesis\/hydrogenation\/chromatography sequence with <jats:bold>11<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (0.0010 M in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>) gives <jats:bold>6<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (5%), <jats:italic>in,out<\/jats:italic>-<jats:bold>2<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (6%), and (<jats:italic>in,in<\/jats:italic>\/<jats:italic>out,out<\/jats:italic>)-<jats:bold>2<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> (7%). Despite the doubled yield of <jats:bold>2<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub>, the longer synthesis of <jats:bold>11<\/jats:bold>\u00b72BH<jats:sub>3<\/jats:sub> vs <jats:bold>1<\/jats:bold>\u00b7BH<jats:sub>3<\/jats:sub> renders the two routes a toss-up; neither compares favorably with precious metal templated syntheses.<\/jats:p>","DOI":"10.3762\/bjoc.14.211","type":"journal-article","created":{"date-parts":[[2018,9,7]],"date-time":"2018-09-07T11:55:58Z","timestamp":1536321358000},"page":"2354-2365","source":"Crossref","is-referenced-by-count":8,"title":["Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene 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