S N 2’ versus S N 2 Reactivity: Control of Regioselectivity in Conversions of Baylis–Hillman Adducts
TiCl 4 ‐induced Baylis–Hillman reactions of α,β‐unsaturated carbonyl compounds with aldehydes yield the ( Z )‐2‐(chloromethyl)vinyl carbonyl compounds 5 , which react with 1,4‐diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions 6 . Their combination with les...
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| Veröffentlicht in: | Chemistry : a European journal 2010-01, Vol.16 (4), p.1365-1371 |
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| container_title | Chemistry : a European journal |
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| creator | Baidya, Mahiuddin Remennikov, Grygoriy Y. Mayer, Peter Mayr, Herbert |
| description | TiCl
4
‐induced Baylis–Hillman reactions of α,β‐unsaturated carbonyl compounds with aldehydes yield the (
Z
)‐2‐(chloromethyl)vinyl carbonyl compounds
5
, which react with 1,4‐diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions
6
. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives
8
under kinetically controlled conditions (S
N
2’ reactions). When more than one equivalent of the carbanions is used, a second S
N
2’ reaction converts
8
into their thermodynamically more stable allyl isomers
9
. The second‐order rate constants for the reactions of
6
with carbanions have been determined photometrically in DMSO. With these rate constants and the previously reported nucleophile‐specific parameters
N
and
s
for the stabilized carbanions, the correlation log
k
(20 °C)=
s
(
N
+
E
) allowed us to calculate the electrophilicity parameters
E
for the allylammonium ions
6
(−19<
E |
| doi_str_mv | 10.1002/chem.200902487 |
| format | Article |
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4
‐induced Baylis–Hillman reactions of α,β‐unsaturated carbonyl compounds with aldehydes yield the (
Z
)‐2‐(chloromethyl)vinyl carbonyl compounds
5
, which react with 1,4‐diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions
6
. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives
8
under kinetically controlled conditions (S
N
2’ reactions). When more than one equivalent of the carbanions is used, a second S
N
2’ reaction converts
8
into their thermodynamically more stable allyl isomers
9
. The second‐order rate constants for the reactions of
6
with carbanions have been determined photometrically in DMSO. With these rate constants and the previously reported nucleophile‐specific parameters
N
and
s
for the stabilized carbanions, the correlation log
k
(20 °C)=
s
(
N
+
E
) allowed us to calculate the electrophilicity parameters
E
for the allylammonium ions
6
(−19<
E
<−18). The kinetic data indicate the S
N
2’ reactions to proceed via an addition–elimination mechanism with a rate‐determining addition step.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.200902487</identifier><language>eng</language><ispartof>Chemistry : a European journal, 2010-01, Vol.16 (4), p.1365-1371</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c847-c6a14491a9217ad249fbd3fc84523a41fecef7c44570d1c5af9a2b7392c7b12f3</citedby><cites>FETCH-LOGICAL-c847-c6a14491a9217ad249fbd3fc84523a41fecef7c44570d1c5af9a2b7392c7b12f3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Baidya, Mahiuddin</creatorcontrib><creatorcontrib>Remennikov, Grygoriy Y.</creatorcontrib><creatorcontrib>Mayer, Peter</creatorcontrib><creatorcontrib>Mayr, Herbert</creatorcontrib><title>S N 2’ versus S N 2 Reactivity: Control of Regioselectivity in Conversions of Baylis–Hillman Adducts</title><title>Chemistry : a European journal</title><description>TiCl
4
‐induced Baylis–Hillman reactions of α,β‐unsaturated carbonyl compounds with aldehydes yield the (
Z
)‐2‐(chloromethyl)vinyl carbonyl compounds
5
, which react with 1,4‐diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions
6
. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives
8
under kinetically controlled conditions (S
N
2’ reactions). When more than one equivalent of the carbanions is used, a second S
N
2’ reaction converts
8
into their thermodynamically more stable allyl isomers
9
. The second‐order rate constants for the reactions of
6
with carbanions have been determined photometrically in DMSO. With these rate constants and the previously reported nucleophile‐specific parameters
N
and
s
for the stabilized carbanions, the correlation log
k
(20 °C)=
s
(
N
+
E
) allowed us to calculate the electrophilicity parameters
E
for the allylammonium ions
6
(−19<
E
<−18). The kinetic data indicate the S
N
2’ reactions to proceed via an addition–elimination mechanism with a rate‐determining addition step.</description><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><recordid>eNo9kE1OwzAQRi0EEqGwZe0LJPg3rtmVCChSBRJ0HzmOTY2SGNlppex6B1ZcrychgYrVaOZ9Mxo9AK4xyjBC5EZvTJsRhCQibC5OQII5wSkVOT8FCZJMpDmn8hxcxPiBxlhOaQI2b_AZksP-G-5MiNsIf3v4apTu3c71wy0sfNcH30Bvx_G789E05gih6yY8rTrfxSlyp4bGxcP-a-maplUdXNT1VvfxEpxZ1URzdawzsH64XxfLdPXy-FQsVqmejx_qXGHGJFaSYKFqwqStampHxglVDFujjRWaMS5QjTVXVipSCSqJFhUmls5A9ndWBx9jMLb8DK5VYSgxKidN5aSp_NdEfwDeRF2s</recordid><startdate>20100125</startdate><enddate>20100125</enddate><creator>Baidya, Mahiuddin</creator><creator>Remennikov, Grygoriy Y.</creator><creator>Mayer, Peter</creator><creator>Mayr, Herbert</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20100125</creationdate><title>S N 2’ versus S N 2 Reactivity: Control of Regioselectivity in Conversions of Baylis–Hillman Adducts</title><author>Baidya, Mahiuddin ; Remennikov, Grygoriy Y. ; Mayer, Peter ; Mayr, Herbert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c847-c6a14491a9217ad249fbd3fc84523a41fecef7c44570d1c5af9a2b7392c7b12f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Baidya, Mahiuddin</creatorcontrib><creatorcontrib>Remennikov, Grygoriy Y.</creatorcontrib><creatorcontrib>Mayer, Peter</creatorcontrib><creatorcontrib>Mayr, Herbert</creatorcontrib><collection>CrossRef</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Baidya, Mahiuddin</au><au>Remennikov, Grygoriy Y.</au><au>Mayer, Peter</au><au>Mayr, Herbert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>S N 2’ versus S N 2 Reactivity: Control of Regioselectivity in Conversions of Baylis–Hillman Adducts</atitle><jtitle>Chemistry : a European journal</jtitle><date>2010-01-25</date><risdate>2010</risdate><volume>16</volume><issue>4</issue><spage>1365</spage><epage>1371</epage><pages>1365-1371</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>TiCl
4
‐induced Baylis–Hillman reactions of α,β‐unsaturated carbonyl compounds with aldehydes yield the (
Z
)‐2‐(chloromethyl)vinyl carbonyl compounds
5
, which react with 1,4‐diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions
6
. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives
8
under kinetically controlled conditions (S
N
2’ reactions). When more than one equivalent of the carbanions is used, a second S
N
2’ reaction converts
8
into their thermodynamically more stable allyl isomers
9
. The second‐order rate constants for the reactions of
6
with carbanions have been determined photometrically in DMSO. With these rate constants and the previously reported nucleophile‐specific parameters
N
and
s
for the stabilized carbanions, the correlation log
k
(20 °C)=
s
(
N
+
E
) allowed us to calculate the electrophilicity parameters
E
for the allylammonium ions
6
(−19<
E
<−18). The kinetic data indicate the S
N
2’ reactions to proceed via an addition–elimination mechanism with a rate‐determining addition step.</abstract><doi>10.1002/chem.200902487</doi><tpages>7</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0947-6539 |
| ispartof | Chemistry : a European journal, 2010-01, Vol.16 (4), p.1365-1371 |
| issn | 0947-6539 1521-3765 |
| language | eng |
| recordid | cdi_crossref_primary_10_1002_chem_200902487 |
| source | Wiley Online Library Journals Frontfile Complete |
| title | S N 2’ versus S N 2 Reactivity: Control of Regioselectivity in Conversions of Baylis–Hillman Adducts |
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