A borrowing hydrogen methodology: palladium-catalyzed dehydrative N -benzylation of 2-aminopyridines in water
We demonstrate a greener borrowing hydrogen methodology using the π-benzylpalladium system, which offers an efficient and environmentally friendly dehydrative N -monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α- d 2 alcohol...
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| Veröffentlicht in: | Green chemistry : an international journal and green chemistry resource : GC 2018, Vol.20 (13), p.3044-3049 |
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| container_title | Green chemistry : an international journal and green chemistry resource : GC |
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| creator | Hikawa, Hidemasa Imamura, Hirokazu Kikkawa, Shoko Azumaya, Isao |
| description | We demonstrate a greener borrowing hydrogen methodology using the π-benzylpalladium system, which offers an efficient and environmentally friendly dehydrative
N
-monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α-
d
2
alcohol and 3-methylbenzyl alcohol afforded H/D scrambled products, suggesting that the dehydrative
N
-benzylation in our catalytic system involves a borrowing hydrogen pathway. KIE experiments show that C–H bond cleavage at the benzylic position of benzyl alcohol is involved in the rate-determining step (KIE = 2.9). This simple base-free protocol can be achieved under mild conditions in an atom-economic process, affording the desired products in moderate to excellent yields. |
| doi_str_mv | 10.1039/C8GC01028E |
| format | Article |
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N
-monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α-
d
2
alcohol and 3-methylbenzyl alcohol afforded H/D scrambled products, suggesting that the dehydrative
N
-benzylation in our catalytic system involves a borrowing hydrogen pathway. KIE experiments show that C–H bond cleavage at the benzylic position of benzyl alcohol is involved in the rate-determining step (KIE = 2.9). This simple base-free protocol can be achieved under mild conditions in an atom-economic process, affording the desired products in moderate to excellent yields.</description><identifier>ISSN: 1463-9262</identifier><identifier>EISSN: 1463-9270</identifier><identifier>DOI: 10.1039/C8GC01028E</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Alcohol ; Alcohols ; Atom economy ; Benzyl alcohol ; Catalysis ; Dehydration ; Green chemistry ; Hydrogen ; Hydrogen bonds ; Palladium</subject><ispartof>Green chemistry : an international journal and green chemistry resource : GC, 2018, Vol.20 (13), p.3044-3049</ispartof><rights>Copyright Royal Society of Chemistry 2018</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c362t-e05da0af92a71f5be10f71605f87da38a9e5bc05f8f124de325148fff4987b063</citedby><cites>FETCH-LOGICAL-c362t-e05da0af92a71f5be10f71605f87da38a9e5bc05f8f124de325148fff4987b063</cites><orcidid>0000-0002-9390-5671 ; 0000-0002-7819-3012 ; 0000-0002-6651-2768</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,4009,27902,27903,27904</link.rule.ids></links><search><creatorcontrib>Hikawa, Hidemasa</creatorcontrib><creatorcontrib>Imamura, Hirokazu</creatorcontrib><creatorcontrib>Kikkawa, Shoko</creatorcontrib><creatorcontrib>Azumaya, Isao</creatorcontrib><title>A borrowing hydrogen methodology: palladium-catalyzed dehydrative N -benzylation of 2-aminopyridines in water</title><title>Green chemistry : an international journal and green chemistry resource : GC</title><description>We demonstrate a greener borrowing hydrogen methodology using the π-benzylpalladium system, which offers an efficient and environmentally friendly dehydrative
N
-monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α-
d
2
alcohol and 3-methylbenzyl alcohol afforded H/D scrambled products, suggesting that the dehydrative
N
-benzylation in our catalytic system involves a borrowing hydrogen pathway. KIE experiments show that C–H bond cleavage at the benzylic position of benzyl alcohol is involved in the rate-determining step (KIE = 2.9). This simple base-free protocol can be achieved under mild conditions in an atom-economic process, affording the desired products in moderate to excellent yields.</description><subject>Alcohol</subject><subject>Alcohols</subject><subject>Atom economy</subject><subject>Benzyl alcohol</subject><subject>Catalysis</subject><subject>Dehydration</subject><subject>Green chemistry</subject><subject>Hydrogen</subject><subject>Hydrogen bonds</subject><subject>Palladium</subject><issn>1463-9262</issn><issn>1463-9270</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpFkF1LwzAYhYMoOKc3_oKAd0I0H_1IvRtlTmHojV6XtHmzZbRJTTtH9-ttmejVeQ_n4T1wELpl9IFRkT3mcpVTRrlcnqEZixJBMp7S87874Zfoqut2lDKWJtEMNQtc-hD8wboN3g46-A043EC_9drXfjM84VbVtdJ235BK9aoejqCxholVvf0G_IZJCe441KP1DnuDOVGNdb4dgtXWQYetwwfVQ7hGF0bVHdz86hx9Pi8_8heyfl-95os1qUTCewI01ooqk3GVMhOXwKhJWUJjI1OthFQZxGU1WcN4pEHwmEXSGBNlMi1pIubo7vS3Df5rD11f7Pw-uLGy4GNMU8kzNlL3J6oKvusCmKINtlFhKBgtpjmL_znFD666aP0</recordid><startdate>2018</startdate><enddate>2018</enddate><creator>Hikawa, Hidemasa</creator><creator>Imamura, Hirokazu</creator><creator>Kikkawa, Shoko</creator><creator>Azumaya, Isao</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7ST</scope><scope>7U6</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-9390-5671</orcidid><orcidid>https://orcid.org/0000-0002-7819-3012</orcidid><orcidid>https://orcid.org/0000-0002-6651-2768</orcidid></search><sort><creationdate>2018</creationdate><title>A borrowing hydrogen methodology: palladium-catalyzed dehydrative N -benzylation of 2-aminopyridines in water</title><author>Hikawa, Hidemasa ; Imamura, Hirokazu ; Kikkawa, Shoko ; Azumaya, Isao</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c362t-e05da0af92a71f5be10f71605f87da38a9e5bc05f8f124de325148fff4987b063</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Alcohol</topic><topic>Alcohols</topic><topic>Atom economy</topic><topic>Benzyl alcohol</topic><topic>Catalysis</topic><topic>Dehydration</topic><topic>Green chemistry</topic><topic>Hydrogen</topic><topic>Hydrogen bonds</topic><topic>Palladium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hikawa, Hidemasa</creatorcontrib><creatorcontrib>Imamura, Hirokazu</creatorcontrib><creatorcontrib>Kikkawa, Shoko</creatorcontrib><creatorcontrib>Azumaya, Isao</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Environment Abstracts</collection><collection>Sustainability Science Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Materials Research Database</collection><jtitle>Green chemistry : an international journal and green chemistry resource : GC</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hikawa, Hidemasa</au><au>Imamura, Hirokazu</au><au>Kikkawa, Shoko</au><au>Azumaya, Isao</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A borrowing hydrogen methodology: palladium-catalyzed dehydrative N -benzylation of 2-aminopyridines in water</atitle><jtitle>Green chemistry : an international journal and green chemistry resource : GC</jtitle><date>2018</date><risdate>2018</risdate><volume>20</volume><issue>13</issue><spage>3044</spage><epage>3049</epage><pages>3044-3049</pages><issn>1463-9262</issn><eissn>1463-9270</eissn><abstract>We demonstrate a greener borrowing hydrogen methodology using the π-benzylpalladium system, which offers an efficient and environmentally friendly dehydrative
N
-monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α-
d
2
alcohol and 3-methylbenzyl alcohol afforded H/D scrambled products, suggesting that the dehydrative
N
-benzylation in our catalytic system involves a borrowing hydrogen pathway. KIE experiments show that C–H bond cleavage at the benzylic position of benzyl alcohol is involved in the rate-determining step (KIE = 2.9). This simple base-free protocol can be achieved under mild conditions in an atom-economic process, affording the desired products in moderate to excellent yields.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/C8GC01028E</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-9390-5671</orcidid><orcidid>https://orcid.org/0000-0002-7819-3012</orcidid><orcidid>https://orcid.org/0000-0002-6651-2768</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9262 |
| ispartof | Green chemistry : an international journal and green chemistry resource : GC, 2018, Vol.20 (13), p.3044-3049 |
| issn | 1463-9262 1463-9270 |
| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Alcohol Alcohols Atom economy Benzyl alcohol Catalysis Dehydration Green chemistry Hydrogen Hydrogen bonds Palladium |
| title | A borrowing hydrogen methodology: palladium-catalyzed dehydrative N -benzylation of 2-aminopyridines in water |
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