Protonation‐Assisted Conjugate Addition of Axially Chiral Enolates: Asymmetric Synthesis of Multisubstituted β‐Lactams from α‐Amino Acids
Identifieur interne : 000890 ( Main/Exploration ); précédent : 000889; suivant : 000891Protonation‐Assisted Conjugate Addition of Axially Chiral Enolates: Asymmetric Synthesis of Multisubstituted β‐Lactams from α‐Amino Acids
Auteurs : Tomoyuki Yoshimura ; Masatoshi Takuwa ; Keisuke Tomohara ; Makoto Uyama ; Kazuhiro Hayashi ; Pan Yang ; Ryuichi Hyakutake ; Takahiro Sasamori ; Norihiro Tokitoh ; Takeo Kawabata [Japon]Source :
- Chemistry – A European Journal [ 0947-6539 ] ; 2012-11-26.
English descriptors
- KwdEn :
- Acid derivatives, Alkyl substituent, Asymmetric, Asymmetric synthesis, Available acids, Bond rotation, Ch3cn, Chem, Chiral, Chiral enolates, Chirality, Complex mixture, Conjugate addition, Contiguous tetra, Cyclization, Diastereomer, Diastereomeric, Diastereomeric mixture, Enantioselective manner, Enolate, Enolates, Ester, Ester exchange, Ethyl ester, Etoh, Gmbh, Hplc separation, Intermolecular side reactions, Intramolecular, Intramolecular alkylation, Intramolecular conjugate addition, Kawabata, Kgaa, Metal carbonates, Precursor, Protonation, Racemization, Reaction time, Reversible intramolecular conjugate addition, Rotational barrier, Silyl ketene acetal, Trisubstituted carbon centers, Verlag, Verlag gmbh, Weak base, Weinheim, Weinheim chem.
- Teeft :
- Acid derivatives, Alkyl substituent, Asymmetric, Asymmetric synthesis, Available acids, Bond rotation, Ch3cn, Chem, Chiral, Chiral enolates, Chirality, Complex mixture, Conjugate addition, Contiguous tetra, Cyclization, Diastereomer, Diastereomeric, Diastereomeric mixture, Enantioselective manner, Enolate, Enolates, Ester, Ester exchange, Ethyl ester, Etoh, Gmbh, Hplc separation, Intermolecular side reactions, Intramolecular, Intramolecular alkylation, Intramolecular conjugate addition, Kawabata, Kgaa, Metal carbonates, Precursor, Protonation, Racemization, Reaction time, Reversible intramolecular conjugate addition, Rotational barrier, Silyl ketene acetal, Trisubstituted carbon centers, Verlag, Verlag gmbh, Weak base, Weinheim, Weinheim chem.
Abstract
β‐Lactams with contiguous tetra‐ and trisubstituted carbon centers were prepared in a highly enantioselective manner through 4‐exo‐trig cyclization of axially chiral enolates generated from readily available α‐amino acids. Use of a weak base (metal carbonate) in a protic solvent (EtOH) is the key to the smooth production of β‐lactams. Use of the weak base is expected to generate the axially chiral enolates in a very low concentration, which undergo intramolecular conjugate addition without suffering intermolecular side reactions. Highly strained β‐lactam enolates thus formed through reversible intramolecular conjugate addition (4‐exo‐trig cyclization) of axially chiral enolates undergo prompt protonation by EtOH in the reaction media (not during the work‐up procedure) to give β‐lactams in up to 97 % ee.
Url:
DOI: 10.1002/chem.201201339
Affiliations:
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Hayashi</name></author><author><name sortKey="Yang, Pan" sort="Yang, Pan" uniqKey="Yang P" first="Pan" last="Yang">Pan Yang</name></author><author><name sortKey="Hyakutake, Ryuichi" sort="Hyakutake, Ryuichi" uniqKey="Hyakutake R" first="Ryuichi" last="Hyakutake">Ryuichi Hyakutake</name></author><author><name sortKey="Sasamori, Takahiro" sort="Sasamori, Takahiro" uniqKey="Sasamori T" first="Takahiro" last="Sasamori">Takahiro Sasamori</name></author><author><name sortKey="Tokitoh, Norihiro" sort="Tokitoh, Norihiro" uniqKey="Tokitoh N" first="Norihiro" last="Tokitoh">Norihiro Tokitoh</name></author><author><name sortKey="Kawabata, Takeo" sort="Kawabata, Takeo" uniqKey="Kawabata T" first="Takeo" last="Kawabata">Takeo Kawabata</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:1522BF3736ECDD6ED5783F4FD69B7940F9D87C2D</idno><date when="2012" year="2012">2012</date><idno type="doi">10.1002/chem.201201339</idno><idno 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Tomoyuki" uniqKey="Yoshimura T" first="Tomoyuki" last="Yoshimura">Tomoyuki Yoshimura</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Takuwa, Masatoshi" sort="Takuwa, Masatoshi" uniqKey="Takuwa M" first="Masatoshi" last="Takuwa">Masatoshi Takuwa</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Tomohara, Keisuke" sort="Tomohara, Keisuke" uniqKey="Tomohara K" first="Keisuke" last="Tomohara">Keisuke Tomohara</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Uyama, Makoto" sort="Uyama, Makoto" uniqKey="Uyama M" first="Makoto" last="Uyama">Makoto Uyama</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Hayashi, Kazuhiro" sort="Hayashi, Kazuhiro" uniqKey="Hayashi K" first="Kazuhiro" last="Hayashi">Kazuhiro Hayashi</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Yang, Pan" sort="Yang, Pan" uniqKey="Yang P" first="Pan" last="Yang">Pan Yang</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Hyakutake, Ryuichi" sort="Hyakutake, Ryuichi" uniqKey="Hyakutake R" first="Ryuichi" last="Hyakutake">Ryuichi Hyakutake</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Sasamori, Takahiro" sort="Sasamori, Takahiro" uniqKey="Sasamori T" first="Takahiro" last="Sasamori">Takahiro Sasamori</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Tokitoh, Norihiro" sort="Tokitoh, Norihiro" uniqKey="Tokitoh N" first="Norihiro" last="Tokitoh">Norihiro Tokitoh</name><affiliation><wicri:noCountry code="subField">(+81) 774‐383197</wicri:noCountry></affiliation></author><author><name sortKey="Kawabata, Takeo" sort="Kawabata, Takeo" uniqKey="Kawabata T" first="Takeo" last="Kawabata">Takeo Kawabata</name><affiliation></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Japon</country></affiliation><affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Chemistry – A European Journal</title><title level="j" type="alt">CHEMISTRY - A EUROPEAN JOURNAL</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><biblScope unit="vol">18</biblScope><biblScope unit="issue">48</biblScope><biblScope unit="page" from="15330">15330</biblScope><biblScope unit="page" to="15336">15336</biblScope><biblScope unit="page-count">7</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2012-11-26">2012-11-26</date></imprint><idno type="ISSN">0947-6539</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acid derivatives</term><term>Alkyl substituent</term><term>Asymmetric</term><term>Asymmetric synthesis</term><term>Available acids</term><term>Bond rotation</term><term>Ch3cn</term><term>Chem</term><term>Chiral</term><term>Chiral enolates</term><term>Chirality</term><term>Complex mixture</term><term>Conjugate addition</term><term>Contiguous tetra</term><term>Cyclization</term><term>Diastereomer</term><term>Diastereomeric</term><term>Diastereomeric mixture</term><term>Enantioselective manner</term><term>Enolate</term><term>Enolates</term><term>Ester</term><term>Ester exchange</term><term>Ethyl ester</term><term>Etoh</term><term>Gmbh</term><term>Hplc separation</term><term>Intermolecular side reactions</term><term>Intramolecular</term><term>Intramolecular alkylation</term><term>Intramolecular conjugate addition</term><term>Kawabata</term><term>Kgaa</term><term>Metal carbonates</term><term>Precursor</term><term>Protonation</term><term>Racemization</term><term>Reaction time</term><term>Reversible intramolecular conjugate addition</term><term>Rotational barrier</term><term>Silyl ketene acetal</term><term>Trisubstituted carbon centers</term><term>Verlag</term><term>Verlag gmbh</term><term>Weak base</term><term>Weinheim</term><term>Weinheim chem</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Acid derivatives</term><term>Alkyl substituent</term><term>Asymmetric</term><term>Asymmetric synthesis</term><term>Available acids</term><term>Bond rotation</term><term>Ch3cn</term><term>Chem</term><term>Chiral</term><term>Chiral enolates</term><term>Chirality</term><term>Complex mixture</term><term>Conjugate addition</term><term>Contiguous tetra</term><term>Cyclization</term><term>Diastereomer</term><term>Diastereomeric</term><term>Diastereomeric mixture</term><term>Enantioselective manner</term><term>Enolate</term><term>Enolates</term><term>Ester</term><term>Ester exchange</term><term>Ethyl ester</term><term>Etoh</term><term>Gmbh</term><term>Hplc separation</term><term>Intermolecular side reactions</term><term>Intramolecular</term><term>Intramolecular alkylation</term><term>Intramolecular conjugate addition</term><term>Kawabata</term><term>Kgaa</term><term>Metal carbonates</term><term>Precursor</term><term>Protonation</term><term>Racemization</term><term>Reaction time</term><term>Reversible intramolecular conjugate addition</term><term>Rotational barrier</term><term>Silyl ketene acetal</term><term>Trisubstituted carbon centers</term><term>Verlag</term><term>Verlag gmbh</term><term>Weak base</term><term>Weinheim</term><term>Weinheim chem</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">β‐Lactams with contiguous tetra‐ and trisubstituted carbon centers were prepared in a highly enantioselective manner through 4‐exo‐trig cyclization of axially chiral enolates generated from readily available α‐amino acids. Use of a weak base (metal carbonate) in a protic solvent (EtOH) is the key to the smooth production of β‐lactams. Use of the weak base is expected to generate the axially chiral enolates in a very low concentration, which undergo intramolecular conjugate addition without suffering intermolecular side reactions. Highly strained β‐lactam enolates thus formed through reversible intramolecular conjugate addition (4‐exo‐trig cyclization) of axially chiral enolates undergo prompt protonation by EtOH in the reaction media (not during the work‐up procedure) to give β‐lactams in up to 97 % ee.</div></front></TEI><affiliations><list><country><li>Japon</li></country></list><tree><noCountry><name sortKey="Hayashi, Kazuhiro" sort="Hayashi, Kazuhiro" uniqKey="Hayashi K" first="Kazuhiro" last="Hayashi">Kazuhiro Hayashi</name><name sortKey="Hyakutake, Ryuichi" sort="Hyakutake, Ryuichi" uniqKey="Hyakutake R" first="Ryuichi" last="Hyakutake">Ryuichi Hyakutake</name><name sortKey="Sasamori, Takahiro" sort="Sasamori, Takahiro" uniqKey="Sasamori T" first="Takahiro" last="Sasamori">Takahiro Sasamori</name><name sortKey="Takuwa, Masatoshi" sort="Takuwa, Masatoshi" uniqKey="Takuwa M" first="Masatoshi" last="Takuwa">Masatoshi Takuwa</name><name sortKey="Tokitoh, Norihiro" sort="Tokitoh, Norihiro" uniqKey="Tokitoh N" first="Norihiro" last="Tokitoh">Norihiro Tokitoh</name><name sortKey="Tomohara, Keisuke" sort="Tomohara, Keisuke" uniqKey="Tomohara K" first="Keisuke" last="Tomohara">Keisuke Tomohara</name><name sortKey="Uyama, Makoto" sort="Uyama, Makoto" uniqKey="Uyama M" first="Makoto" last="Uyama">Makoto Uyama</name><name sortKey="Yang, Pan" sort="Yang, Pan" uniqKey="Yang P" first="Pan" last="Yang">Pan Yang</name><name sortKey="Yoshimura, Tomoyuki" sort="Yoshimura, Tomoyuki" uniqKey="Yoshimura T" first="Tomoyuki" last="Yoshimura">Tomoyuki Yoshimura</name></noCountry><country name="Japon"><noRegion><name sortKey="Kawabata, Takeo" sort="Kawabata, Takeo" uniqKey="Kawabata T" first="Takeo" last="Kawabata">Takeo Kawabata</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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