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A Nontemplated Route to Macrocyclic Dibridgehead Diphosphorus Compounds: Crystallographic Characterization of a “Crossed‐Chain” Variant of in/out Stereoisomers
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-08-03 , DOI: 10.1002/asia.201800739 Sugam Kharel 1 , Tiezheng Jia 1 , Nattamai Bhuvanesh 1 , Joseph H Reibenspies 1 , Janet Blümel 1 , John A Gladysz 1
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-08-03 , DOI: 10.1002/asia.201800739 Sugam Kharel 1 , Tiezheng Jia 1 , Nattamai Bhuvanesh 1 , Joseph H Reibenspies 1 , Janet Blümel 1 , John A Gladysz 1
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Reactions of (O=)PH(OCH2CH3)2 and BrMg(CH2)mCH=CH2 (4.9–3.2 equiv; m=4 (a), 5 (b), 6 (c)) give the dialkylphosphine oxides (O=)PH[(CH2)mCH=CH2]2 (2 a–c; 77–81 % after workup), which are treated with NaH and then α,ω‐dibromides Br(CH2)nBr (0.49–0.32 equiv; n=8 (a′), 10 (b′), 12 (c′), 14 (d′)) to yield the bis(trialkylphosphine oxides) [H2C=CH(CH2)m]2P(=O)(CH2)n(O=)P[(CH2)mCH=CH2]2 (3 ab′, 3 bc′, 3 cd′, 3 ca′; 79–84 %). Reactions of 3 bc′ and 3 ca′ with Grubbs’ first‐generation catalyst and then H2/PtO2 afford the dibridgehead diphosphine dioxides 
(4 bc′, 4 ca′; 14–19 %, n′=2m+2); 31P NMR spectra show two stereoisomeric species (ca. 70:30). Crystal structures of two isomers of the latter are obtained, out,out‐4 ca′ and a conformer of in,out‐4 ca′ that features crossed chains, such that the (O=)P vectors appear out,out. Whereas 4 bc′ resists crystallization, a byproduct derived from an alternative metathesis mode, (CH2)12P(=O)(CH2)12(O=)P(CH2)12, as well as 3 ab′ and 3 bc′, are structurally characterized. The efficiencies of other routes to dibridgehead diphosphorus compounds are compared.
中文翻译：
大环双桥头二磷化合物的非模板化途径：输入/输出立体异构体“交叉链”变体的晶体学表征
(O=)PH(OCH 2 CH 3 ) 2和 BrMg(CH 2 ) m CH=CH 2 （4.9–3.2 当量； m =4 ( a ), 5 ( b ), 6 ( c )）的反应给出二烷基氧化膦 (O=)PH[(CH 2 ) m CH=CH 2 ] 2 ( 2 a – c ; 后处理后为 77–81 %)，先用 NaH 处理，然后用 α,ω-二溴化物 Br(CH 2 ) 处理n Br (0.49–0.32 当量； n =8 ( a′ ), 10 ( b′ ), 12 ( c′ ), 14 ( d′ )) 生成双(三烷基氧化膦) [H 2 C=CH(CH 2 ) m ] 2 P(=O)(CH 2 ) n (O=)P[(CH 2 ) m CH=CH 2 ] 2 ( 3 ab' , 3 bc' , 3 cd' , 3 ca' ; 79 –84%）。 3 bc'和3 ca'与 Grubbs 第一代催化剂反应，然后与 H 2 /PtO 2反应，得到双桥头二氧化膦 ( 4 bc′ , 4 ca′ ; 14–19 %, n′ =2 m +2); 31 P NMR 谱显示两种立体异构体（约 70:30）。获得了后者的两个异构体的晶体结构， out , out ‐ 4 ca'和in , out ‐ 4 ca'的构象异构体，其特征是交叉链，使得 (O=)P 向量出现out , out 。 而4 bc'难以结晶，则衍生自替代复分解模式的副产物 ( CH 2 ) 12 P (=O)(CH 2 ) 12 (O=) P(C H 2 ) 12以及3 ab'和3 bc' ，进行了结构表征。比较了双桥头二磷化合物的其他途径的效率。
更新日期：2018-08-03
(4 bc′, 4 ca′; 14–19 %, n′=2m+2); 31P NMR spectra show two stereoisomeric species (ca. 70:30). Crystal structures of two isomers of the latter are obtained, out,out‐4 ca′ and a conformer of in,out‐4 ca′ that features crossed chains, such that the (O=)P vectors appear out,out. Whereas 4 bc′ resists crystallization, a byproduct derived from an alternative metathesis mode, (CH2)12P(=O)(CH2)12(O=)P(CH2)12, as well as 3 ab′ and 3 bc′, are structurally characterized. The efficiencies of other routes to dibridgehead diphosphorus compounds are compared.
中文翻译：
大环双桥头二磷化合物的非模板化途径：输入/输出立体异构体“交叉链”变体的晶体学表征
(O=)PH(OCH 2 CH 3 ) 2和 BrMg(CH 2 ) m CH=CH 2 （4.9–3.2 当量； m =4 ( a ), 5 ( b ), 6 ( c )）的反应给出二烷基氧化膦 (O=)PH[(CH 2 ) m CH=CH 2 ] 2 ( 2 a – c ; 后处理后为 77–81 %)，先用 NaH 处理，然后用 α,ω-二溴化物 Br(CH 2 ) 处理n Br (0.49–0.32 当量； n =8 ( a′ ), 10 ( b′ ), 12 ( c′ ), 14 ( d′ )) 生成双(三烷基氧化膦) [H 2 C=CH(CH 2 ) m ] 2 P(=O)(CH 2 ) n (O=)P[(CH 2 ) m CH=CH 2 ] 2 ( 3 ab' , 3 bc' , 3 cd' , 3 ca' ; 79 –84%）。 3 bc'和3 ca'与 Grubbs 第一代催化剂反应，然后与 H 2 /PtO 2反应，得到双桥头二氧化膦
( 4 bc′ , 4 ca′ ; 14–19 %, n′ =2 m +2); 31 P NMR 谱显示两种立体异构体（约 70:30）。获得了后者的两个异构体的晶体结构， out , out ‐ 4 ca'和in , out ‐ 4 ca'的构象异构体，其特征是交叉链，使得 (O=)P 向量出现out , out 。 而4 bc'难以结晶，则衍生自替代复分解模式的副产物 ( CH 2 ) 12 P (=O)(CH 2 ) 12 (O=) P(C H 2 ) 12以及3 ab'和3 bc' ，进行了结构表征。比较了双桥头二磷化合物的其他途径的效率。
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