Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes
Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the imi...
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| Veröffentlicht in: | Chemistry : a European journal 2013-07, Vol.19 (31), p.10412-10418 |
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| creator | Lindqvist, Markus Axenov, Kirill Nieger, Martin Räisänen, Minna Leskelä, Markku Repo, Timo |
| description | Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C6F5)2 adduct. When the starting enamine is present in excess over HB(C6F5)2, the produced bornylamine–HB(C6F5)2 adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C6F5)2 pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion.
Bor(o)n to be wild: Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers' borane to give the corresponding iminium–hydroborate zwitterionic salt (see scheme). Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. When the starting enamine is present in excess, hydrogenation of the camphor–enamine framework proceeds in a catalytic fashion. |
| doi_str_mv | 10.1002/chem.201300462 |
| format | Article |
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Bor(o)n to be wild: Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers' borane to give the corresponding iminium–hydroborate zwitterionic salt (see scheme). Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. When the starting enamine is present in excess, hydrogenation of the camphor–enamine framework proceeds in a catalytic fashion.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201300462</identifier><identifier>PMID: 23788132</identifier><identifier>CODEN: CEUJED</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Adducts ; Boranes ; boron ; Catalysis ; Catalysts ; Chemistry ; frustrated Lewis pairs ; Hydrogen storage ; Hydrogenation ; nitrogen ; Parents ; Piers ; reaction mechanism</subject><ispartof>Chemistry : a European journal, 2013-07, Vol.19 (31), p.10412-10418</ispartof><rights>Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5102-64dfc402cccc024ef6932177d00d8041706c042a3715b6e4ac065b991ae7b1963</citedby><cites>FETCH-LOGICAL-c5102-64dfc402cccc024ef6932177d00d8041706c042a3715b6e4ac065b991ae7b1963</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.201300462$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201300462$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23788132$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lindqvist, Markus</creatorcontrib><creatorcontrib>Axenov, Kirill</creatorcontrib><creatorcontrib>Nieger, Martin</creatorcontrib><creatorcontrib>Räisänen, Minna</creatorcontrib><creatorcontrib>Leskelä, Markku</creatorcontrib><creatorcontrib>Repo, Timo</creatorcontrib><title>Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C6F5)2 adduct. When the starting enamine is present in excess over HB(C6F5)2, the produced bornylamine–HB(C6F5)2 adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C6F5)2 pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion.
Bor(o)n to be wild: Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers' borane to give the corresponding iminium–hydroborate zwitterionic salt (see scheme). Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. When the starting enamine is present in excess, hydrogenation of the camphor–enamine framework proceeds in a catalytic fashion.</description><subject>Adducts</subject><subject>Boranes</subject><subject>boron</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>frustrated Lewis pairs</subject><subject>Hydrogen storage</subject><subject>Hydrogenation</subject><subject>nitrogen</subject><subject>Parents</subject><subject>Piers</subject><subject>reaction mechanism</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqFkc1LwzAYxoMobn5cPUrBy0Q633w3x1mcE-bHQfEY0jbFznadyYruvzdjOsSLuYSE3_PkyfsgdIJhiAHIZf5qmyEBTAGYIDuojznBMZWC76I-KCZjwanqoQPvZwCgBKX7qEeoTBJMSR9Nxq7zS2eWtoim9qPy0aOpXJQG2yrcr6K2DIfKmToaXJzHqWkWr62Lr4wPglFTzdusdWZu_RHaK03t7fH3foiex9dP6SSePtzcpqNpnHMMJBasKHMGJA8LCLOlUJRgKQuAIgGGJYgcGDFUYp4Jy0wOgmdKYWNlhkP8QzTY-C5c-95Zv9QhaG7rOoRoO6-DVwJYUp78jzKMBZFU8YCe_UFnbefm4SOBCmNTDOT67eGGyl3rvbOlXriqMW6lMeh1HXpdh97WEQSn37Zd1thii__MPwBqA3xUtV39Y6fTyfXdb_N4ow1F2c-t1rg3LSSVXL_c32gp7iQfT5Ue0y9JhqG1</recordid><startdate>20130729</startdate><enddate>20130729</enddate><creator>Lindqvist, Markus</creator><creator>Axenov, Kirill</creator><creator>Nieger, Martin</creator><creator>Räisänen, Minna</creator><creator>Leskelä, Markku</creator><creator>Repo, Timo</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope></search><sort><creationdate>20130729</creationdate><title>Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes</title><author>Lindqvist, Markus ; Axenov, Kirill ; Nieger, Martin ; Räisänen, Minna ; Leskelä, Markku ; Repo, Timo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5102-64dfc402cccc024ef6932177d00d8041706c042a3715b6e4ac065b991ae7b1963</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Adducts</topic><topic>Boranes</topic><topic>boron</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>frustrated Lewis pairs</topic><topic>Hydrogen storage</topic><topic>Hydrogenation</topic><topic>nitrogen</topic><topic>Parents</topic><topic>Piers</topic><topic>reaction mechanism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lindqvist, Markus</creatorcontrib><creatorcontrib>Axenov, Kirill</creatorcontrib><creatorcontrib>Nieger, Martin</creatorcontrib><creatorcontrib>Räisänen, Minna</creatorcontrib><creatorcontrib>Leskelä, Markku</creatorcontrib><creatorcontrib>Repo, Timo</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lindqvist, Markus</au><au>Axenov, Kirill</au><au>Nieger, Martin</au><au>Räisänen, Minna</au><au>Leskelä, Markku</au><au>Repo, Timo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2013-07-29</date><risdate>2013</risdate><volume>19</volume><issue>31</issue><spage>10412</spage><epage>10418</epage><pages>10412-10418</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><coden>CEUJED</coden><abstract>Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C6F5)2 adduct. When the starting enamine is present in excess over HB(C6F5)2, the produced bornylamine–HB(C6F5)2 adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C6F5)2 pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion.
Bor(o)n to be wild: Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers' borane to give the corresponding iminium–hydroborate zwitterionic salt (see scheme). Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. When the starting enamine is present in excess, hydrogenation of the camphor–enamine framework proceeds in a catalytic fashion.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>23788132</pmid><doi>10.1002/chem.201300462</doi><tpages>7</tpages></addata></record> |
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| subjects | Adducts Boranes boron Catalysis Catalysts Chemistry frustrated Lewis pairs Hydrogen storage Hydrogenation nitrogen Parents Piers reaction mechanism |
| title | Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes |
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