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A chiral spiroborate anion from diphenyl-l-tartramide [B{l-Tar(NHPh)2}2]− applied to some challenging resolutions†
CrystEngComm ( IF 3.1 ) Pub Date : 2018-07-14 00:00:00 , DOI: 10.1039/c8ce00855h Lawrence W.-Y. Wong 1, 2, 3, 4 , Gemma S.-S. Tam 1, 2, 3, 4 , Xiaoyan Chen 1, 2, 3, 4 , Frederick T.-K. So 1, 2, 3, 4 , Aristyo Soecipto 1, 2, 3, 4 , Fu Kit Sheong 1, 2, 3, 4 , Herman H.-Y. Sung 1, 2, 3, 4 , Zhenyang Lin 1, 2, 3, 4 , Ian D. Williams 1, 2, 3, 4
CrystEngComm ( IF 3.1 ) Pub Date : 2018-07-14 00:00:00 , DOI: 10.1039/c8ce00855h Lawrence W.-Y. Wong 1, 2, 3, 4 , Gemma S.-S. Tam 1, 2, 3, 4 , Xiaoyan Chen 1, 2, 3, 4 , Frederick T.-K. So 1, 2, 3, 4 , Aristyo Soecipto 1, 2, 3, 4 , Fu Kit Sheong 1, 2, 3, 4 , Herman H.-Y. Sung 1, 2, 3, 4 , Zhenyang Lin 1, 2, 3, 4 , Ian D. Williams 1, 2, 3, 4
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The chiral spiroborate anion [B{L-Tar(NHPh)2}2]− has been prepared as simple salts K, NH4, Na in high yield and purity. Its structural features have been examined by single crystal XRD and DFT calculations and indicate that conformational arrangements are dominated by intramolecular NH---O![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C inter-amide hydrogen bonds. These confer predictable shape, as well as a clear binding site for ion-pair formation. The potential of this anion for resolution by diastereomeric salt formation was then tested using five challenging racemic amines of type NH2CHR1R2 with high shape similarity between their enantiomers. Organo-ammonium salts from these were made directly from a simple 1-pot reaction from racemic amine, boric acid and 2 eq. N,N′-diphenyl-L-tartramide in MeOH. The products are single phase crystalline solids with moderate to excellent enantioexcesses up to 95% ee. They show conserved NH3R+ binding and layered packing arrangements, all with short 5.5 Å axes. Based on chiral HPLC the initial [B{L-Tar(NHPh)2}2] salt from rac-phenylglycinol has [S-NH3CH(CH2OH)Ph]+ with 95% ee and the salt from rac-1-phenylpropylamine is also well resolved (>91% ee) in a single step. Three disorder modes that limit resolution in the other salts were identified at the cation site – H/R1 site exchange, R1/R2 site exchange or C–H re-pyramidalization. Extension to a family of such aryltartramide anions may allow crystal engineering of the cation binding pockets to overcome the disorder inherent to such resolutions.
中文翻译：
来自二苯基-1-酒石酰胺[B { l -Tar（NHPh）2 } 2 ] -的手性螺硼酸根阴离子应用于一些具有挑战性的解决方案†
手性螺硼酸根阴离子[B { L -Tar（NHPh）2 } 2 ] -以高收率和高纯度制备为简单的盐K，NH 4，Na。它的结构特征已通过单晶XRD和DFT计算进行了检验，表明构象排列主要由分子内NH--OC酰胺间氢键控制。这些赋予可预测的形状，以及用于离子对形成的清晰结合位点。然后使用五种具有挑战性的NH 2 CHR 1 R 2型外消旋胺测试了该阴离子通过非对映异构体形成盐而分解的潜力。它们的对映异构体之间具有高度的形状相似性。来自这些的有机铵盐直接由消旋胺，硼酸和2 eq。的简单的1-pot反应直接制得。N，N'-二苯基-L-酒石酰胺在MeOH中。产品为单相结晶固体，对映体过量中等至极好，ee最高可达95％。它们显示了保守的NH 3 R +结合和分层堆积排列，所有轴的长度均为5.5Å。基于手性HPLC，来自外消旋-苯基甘醇的初始[B { L -Tar（NHPh）2 } 2 ]盐具有[S-NH 3 CH（CH 2 OH）Ph] +一步法分离含有95％ee的rac和rac -1-苯基丙胺的盐（> 91％ee）。在阳离子位点上发现了三种限制其他盐类拆分的无序模式-H / R 1位点交换，R 1 / R 2位点交换或CHH重新金字塔化。扩展到这类芳基酒石酰胺阴离子家族可允许阳离子结合口袋的晶体工程化，以克服此类拆分所固有的障碍。
更新日期：2018-07-14
C inter-amide hydrogen bonds. These confer predictable shape, as well as a clear binding site for ion-pair formation. The potential of this anion for resolution by diastereomeric salt formation was then tested using five challenging racemic amines of type NH2CHR1R2 with high shape similarity between their enantiomers. Organo-ammonium salts from these were made directly from a simple 1-pot reaction from racemic amine, boric acid and 2 eq. N,N′-diphenyl-L-tartramide in MeOH. The products are single phase crystalline solids with moderate to excellent enantioexcesses up to 95% ee. They show conserved NH3R+ binding and layered packing arrangements, all with short 5.5 Å axes. Based on chiral HPLC the initial [B{L-Tar(NHPh)2}2] salt from rac-phenylglycinol has [S-NH3CH(CH2OH)Ph]+ with 95% ee and the salt from rac-1-phenylpropylamine is also well resolved (>91% ee) in a single step. Three disorder modes that limit resolution in the other salts were identified at the cation site – H/R1 site exchange, R1/R2 site exchange or C–H re-pyramidalization. Extension to a family of such aryltartramide anions may allow crystal engineering of the cation binding pockets to overcome the disorder inherent to such resolutions.
中文翻译：
来自二苯基-1-酒石酰胺[B { l -Tar（NHPh）2 } 2 ] -的手性螺硼酸根阴离子应用于一些具有挑战性的解决方案†
手性螺硼酸根阴离子[B { L -Tar（NHPh）2 } 2 ] -以高收率和高纯度制备为简单的盐K，NH 4，Na。它的结构特征已通过单晶XRD和DFT计算进行了检验，表明构象排列主要由分子内NH--
OC酰胺间氢键控制。这些赋予可预测的形状，以及用于离子对形成的清晰结合位点。然后使用五种具有挑战性的NH 2 CHR 1 R 2型外消旋胺测试了该阴离子通过非对映异构体形成盐而分解的潜力。它们的对映异构体之间具有高度的形状相似性。来自这些的有机铵盐直接由消旋胺，硼酸和2 eq。的简单的1-pot反应直接制得。N，N'-二苯基-L-酒石酰胺在MeOH中。产品为单相结晶固体，对映体过量中等至极好，ee最高可达95％。它们显示了保守的NH 3 R +结合和分层堆积排列，所有轴的长度均为5.5Å。基于手性HPLC，来自外消旋-苯基甘醇的初始[B { L -Tar（NHPh）2 } 2 ]盐具有[S-NH 3 CH（CH 2 OH）Ph] +一步法分离含有95％ee的rac和rac -1-苯基丙胺的盐（> 91％ee）。在阳离子位点上发现了三种限制其他盐类拆分的无序模式-H / R 1位点交换，R 1 / R 2位点交换或CHH重新金字塔化。扩展到这类芳基酒石酰胺阴离子家族可允许阳离子结合口袋的晶体工程化，以克服此类拆分所固有的障碍。
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