Crystal engineering rescues a solution organic synthesis in a cocrystallization that confirms the configuration of a molecular ladder
Treatment of an achiral molecular ladder of Câh symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate tw...
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| Veröffentlicht in: | Proceedings of the National Academy of Sciences - PNAS 2011-07, Vol.108 (27), p.10974-10979 |
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| creator | Atkinson, Manza B.J Mariappan, S.V. Santhana BuÄar, Dejan-KreÅ¡imir Baltrusaitis, Jonas FriÅ¡ÄiÄ, Tomislav Sinada, Naif G MacGillivray, Leonard R |
| description | Treatment of an achiral molecular ladder of Câh symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate two diastereomers. The NMR data, however, could not lead to unambiguous configurational assignments of the two isomers. Single-crystal X-ray diffraction was employed to determine each configuration. One isomer readily crystallized as a pure form and X-ray diffraction revealed the molecule as being achiral based on Ci symmetry. The second isomer resisted crystallization under a variety of conditions. Consequently, a strategy based on a cocrystallization was developed to generate single crystals of the second isomer. Cocrystallization of the isomer with a carboxylic acid readily afforded single crystals that confirmed a chiral ladderane based on Câ symmetry. The chiral ladderane and acid self-assembled to generate a five-component hydrogen-bonded complex that packs to form large solvent-filled homochiral channels of nanometer-scale dimensions. Whereas cocrystallizations are frequently applied to structure determinations of proteins, our study represents the first application of a cocrystallization to confirm the relative configuration of a small-molecule diastereomer generated in a solution-phase organic synthesis. |
| doi_str_mv | 10.1073/pnas.1104352108 |
| format | Article |
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Santhana ; BuÄar, Dejan-KreÅ¡imir ; Baltrusaitis, Jonas ; FriÅ¡ÄiÄ, Tomislav ; Sinada, Naif G ; MacGillivray, Leonard R</creator><creatorcontrib>Atkinson, Manza B.J ; Mariappan, S.V. Santhana ; BuÄar, Dejan-KreÅ¡imir ; Baltrusaitis, Jonas ; FriÅ¡ÄiÄ, Tomislav ; Sinada, Naif G ; MacGillivray, Leonard R</creatorcontrib><description>Treatment of an achiral molecular ladder of Câh symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate two diastereomers. The NMR data, however, could not lead to unambiguous configurational assignments of the two isomers. Single-crystal X-ray diffraction was employed to determine each configuration. One isomer readily crystallized as a pure form and X-ray diffraction revealed the molecule as being achiral based on Ci symmetry. The second isomer resisted crystallization under a variety of conditions. Consequently, a strategy based on a cocrystallization was developed to generate single crystals of the second isomer. Cocrystallization of the isomer with a carboxylic acid readily afforded single crystals that confirmed a chiral ladderane based on Câ symmetry. The chiral ladderane and acid self-assembled to generate a five-component hydrogen-bonded complex that packs to form large solvent-filled homochiral channels of nanometer-scale dimensions. Whereas cocrystallizations are frequently applied to structure determinations of proteins, our study represents the first application of a cocrystallization to confirm the relative configuration of a small-molecule diastereomer generated in a solution-phase organic synthesis.</description><identifier>ISSN: 0027-8424</identifier><identifier>EISSN: 1091-6490</identifier><identifier>DOI: 10.1073/pnas.1104352108</identifier><identifier>PMID: 21690362</identifier><language>eng</language><publisher>United States: National Academy of Sciences</publisher><subject>Carboxylic acids ; Crystallization ; Crystals ; diastereomers ; Diffraction ; engineering ; hydrogen bonding ; Hydrogen bonds ; Isomerization ; Isomers ; molecular conformation ; Molecules ; NMR ; Nuclear magnetic resonance ; nuclear magnetic resonance spectroscopy ; Physical Sciences ; proteins ; Single crystals ; Solvents ; Spectroscopy ; Synthetic chemistry techniques ; X-ray diffraction</subject><ispartof>Proceedings of the National Academy of Sciences - PNAS, 2011-07, Vol.108 (27), p.10974-10979</ispartof><rights>copyright © 1993–2008 National Academy of Sciences of the United States of America</rights><rights>Copyright National Academy of Sciences Jul 5, 2011</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c490t-2b56f577cdd37251bd8e3b73d59504e6d17385d90631a2176ab585a142d004a3</citedby><cites>FETCH-LOGICAL-c490t-2b56f577cdd37251bd8e3b73d59504e6d17385d90631a2176ab585a142d004a3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Uhttp://www.pnas.org/content/108/27.cover.gif</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/27978727$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/27978727$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,723,776,780,799,881,27901,27902,53766,53768,57992,58225</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21690362$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Atkinson, Manza B.J</creatorcontrib><creatorcontrib>Mariappan, S.V. Santhana</creatorcontrib><creatorcontrib>BuÄar, Dejan-KreÅ¡imir</creatorcontrib><creatorcontrib>Baltrusaitis, Jonas</creatorcontrib><creatorcontrib>FriÅ¡ÄiÄ, Tomislav</creatorcontrib><creatorcontrib>Sinada, Naif G</creatorcontrib><creatorcontrib>MacGillivray, Leonard R</creatorcontrib><title>Crystal engineering rescues a solution organic synthesis in a cocrystallization that confirms the configuration of a molecular ladder</title><title>Proceedings of the National Academy of Sciences - PNAS</title><addtitle>Proc Natl Acad Sci U S A</addtitle><description>Treatment of an achiral molecular ladder of Câh symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate two diastereomers. The NMR data, however, could not lead to unambiguous configurational assignments of the two isomers. Single-crystal X-ray diffraction was employed to determine each configuration. One isomer readily crystallized as a pure form and X-ray diffraction revealed the molecule as being achiral based on Ci symmetry. The second isomer resisted crystallization under a variety of conditions. Consequently, a strategy based on a cocrystallization was developed to generate single crystals of the second isomer. Cocrystallization of the isomer with a carboxylic acid readily afforded single crystals that confirmed a chiral ladderane based on Câ symmetry. The chiral ladderane and acid self-assembled to generate a five-component hydrogen-bonded complex that packs to form large solvent-filled homochiral channels of nanometer-scale dimensions. Whereas cocrystallizations are frequently applied to structure determinations of proteins, our study represents the first application of a cocrystallization to confirm the relative configuration of a small-molecule diastereomer generated in a solution-phase organic synthesis.</description><subject>Carboxylic acids</subject><subject>Crystallization</subject><subject>Crystals</subject><subject>diastereomers</subject><subject>Diffraction</subject><subject>engineering</subject><subject>hydrogen bonding</subject><subject>Hydrogen bonds</subject><subject>Isomerization</subject><subject>Isomers</subject><subject>molecular conformation</subject><subject>Molecules</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>nuclear magnetic resonance spectroscopy</subject><subject>Physical Sciences</subject><subject>proteins</subject><subject>Single crystals</subject><subject>Solvents</subject><subject>Spectroscopy</subject><subject>Synthetic chemistry techniques</subject><subject>X-ray diffraction</subject><issn>0027-8424</issn><issn>1091-6490</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><recordid>eNpdkc2P0zAQxS0EYsvCmRMQceGU3fFX7FxWQhVf0kocWM6WYzupq9QudoJU7vzfuKRsAfkwGr_fPHn8EHqO4QqDoNf7oPMVxsAoJxjkA7TC0OK6YS08RCsAImrJCLtAT3LeAkDLJTxGFwQ3LdCGrNDPdTrkSY-VC4MPziUfhiq5bGaXK13lOM6Tj6GKadDBmyofwrRx2efKh6KbaJb50f_Qv8Fpo6dyHXqfdrl0bmmGOS167MvYLo7OzKNO1aitdekpetTrMbtnp3qJ7t6_u1t_rG8_f_i0fntbm7LQVJOONz0XwlhLBeG4s9LRTlDLWw7MNRYLKrltoaFYEywa3XHJNWbEAjBNL9HNYrufu52zxoUp6VHtk9_pdFBRe_WvEvxGDfG7oricBorBm5NBit_KD01q57Nx46iDi3NWUnAmZct4IV__R27jnEJZ7ghxQglvCnS9QCbFnJPr75-CQR3zVcd81TnfMvHy7w3u-T-BFqA6AcfJs51URJTSClaQFwuyzVNMZwvRCimIKPqrRe91VHpIPquvXwjgBgC3BDinvwB6asGa</recordid><startdate>20110705</startdate><enddate>20110705</enddate><creator>Atkinson, Manza B.J</creator><creator>Mariappan, S.V. 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Santhana ; BuÄar, Dejan-KreÅ¡imir ; Baltrusaitis, Jonas ; FriÅ¡ÄiÄ, Tomislav ; Sinada, Naif G ; MacGillivray, Leonard R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c490t-2b56f577cdd37251bd8e3b73d59504e6d17385d90631a2176ab585a142d004a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Carboxylic acids</topic><topic>Crystallization</topic><topic>Crystals</topic><topic>diastereomers</topic><topic>Diffraction</topic><topic>engineering</topic><topic>hydrogen bonding</topic><topic>Hydrogen bonds</topic><topic>Isomerization</topic><topic>Isomers</topic><topic>molecular conformation</topic><topic>Molecules</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>nuclear magnetic resonance spectroscopy</topic><topic>Physical Sciences</topic><topic>proteins</topic><topic>Single crystals</topic><topic>Solvents</topic><topic>Spectroscopy</topic><topic>Synthetic chemistry techniques</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Atkinson, Manza B.J</creatorcontrib><creatorcontrib>Mariappan, S.V. 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Santhana</au><au>BuÄar, Dejan-KreÅ¡imir</au><au>Baltrusaitis, Jonas</au><au>FriÅ¡ÄiÄ, Tomislav</au><au>Sinada, Naif G</au><au>MacGillivray, Leonard R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Crystal engineering rescues a solution organic synthesis in a cocrystallization that confirms the configuration of a molecular ladder</atitle><jtitle>Proceedings of the National Academy of Sciences - PNAS</jtitle><addtitle>Proc Natl Acad Sci U S A</addtitle><date>2011-07-05</date><risdate>2011</risdate><volume>108</volume><issue>27</issue><spage>10974</spage><epage>10979</epage><pages>10974-10979</pages><issn>0027-8424</issn><eissn>1091-6490</eissn><abstract>Treatment of an achiral molecular ladder of Câh symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate two diastereomers. The NMR data, however, could not lead to unambiguous configurational assignments of the two isomers. Single-crystal X-ray diffraction was employed to determine each configuration. One isomer readily crystallized as a pure form and X-ray diffraction revealed the molecule as being achiral based on Ci symmetry. The second isomer resisted crystallization under a variety of conditions. Consequently, a strategy based on a cocrystallization was developed to generate single crystals of the second isomer. Cocrystallization of the isomer with a carboxylic acid readily afforded single crystals that confirmed a chiral ladderane based on Câ symmetry. The chiral ladderane and acid self-assembled to generate a five-component hydrogen-bonded complex that packs to form large solvent-filled homochiral channels of nanometer-scale dimensions. 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| subjects | Carboxylic acids Crystallization Crystals diastereomers Diffraction engineering hydrogen bonding Hydrogen bonds Isomerization Isomers molecular conformation Molecules NMR Nuclear magnetic resonance nuclear magnetic resonance spectroscopy Physical Sciences proteins Single crystals Solvents Spectroscopy Synthetic chemistry techniques X-ray diffraction |
| title | Crystal engineering rescues a solution organic synthesis in a cocrystallization that confirms the configuration of a molecular ladder |
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