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Diastereoselective Photocycloaddition Reaction of Vinyl Ether Tethered to 1,4‐Naphthoquinone
The intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether with a small (R)‐point‐chiral group on the tether was studied. Under photoirradiation, [2+2] cyclobutane products were exclusively obtained for this intramolecular system. The effect of solvent polarity on th...
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Published in: | ChemPhotoChem 2019-05, Vol.3 (5), p.243-250 |
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description | The intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether with a small (R)‐point‐chiral group on the tether was studied. Under photoirradiation, [2+2] cyclobutane products were exclusively obtained for this intramolecular system. The effect of solvent polarity on the stereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. The detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes, which were switched between the ground‐state equilibrium, the relative rate of bond formation in the triplet manifold, as well as deactivation processes between the pro‐(S3) and pro‐(R3) precursors, depending on the temperature domain examined. The enthalpic contribution (ΔΔH≠) was always compensated by the entropic factor (ΔΔS≠), implying the importance of solvation on the diastereo‐differentiation steps. The mechanism of photocycloaddition, especially for the face‐selective processes, is thoroughly discussed, which is supported by quantum chemical calculations on the ground‐state circular dichroism (CD) spectral behavior as well as on the diastereomeric transition states in the triplet excited state.
Poles apart: In an intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether, the effect of solvent polarity on the diastereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. A detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes. |
doi_str_mv | 10.1002/cptc.201900022 |
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Poles apart: In an intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether, the effect of solvent polarity on the diastereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. A detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes.</description><identifier>ISSN: 2367-0932</identifier><identifier>EISSN: 2367-0932</identifier><identifier>DOI: 10.1002/cptc.201900022</identifier><language>eng</language><subject>1,4-naphthoquinone ; asymmetric synthesis ; cycloaddition reactions ; diastereoselectivity ; triplet excited states ; vinyl ether</subject><ispartof>ChemPhotoChem, 2019-05, Vol.3 (5), p.243-250</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3552-ca068164d0794ac801f348fb882026610e0428e9b6bd1fbc2eba7855c4e550e33</citedby><cites>FETCH-LOGICAL-c3552-ca068164d0794ac801f348fb882026610e0428e9b6bd1fbc2eba7855c4e550e33</cites><orcidid>0000-0003-3918-0873</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Ishikawa, Hiroki</creatorcontrib><creatorcontrib>Chung, Tim S.</creatorcontrib><creatorcontrib>Fukuhara, Gaku</creatorcontrib><creatorcontrib>Shigemitsu, Hajime</creatorcontrib><creatorcontrib>Kida, Toshiyuki</creatorcontrib><creatorcontrib>Bach, Thorsten</creatorcontrib><creatorcontrib>Mori, Tadashi</creatorcontrib><title>Diastereoselective Photocycloaddition Reaction of Vinyl Ether Tethered to 1,4‐Naphthoquinone</title><title>ChemPhotoChem</title><description>The intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether with a small (R)‐point‐chiral group on the tether was studied. Under photoirradiation, [2+2] cyclobutane products were exclusively obtained for this intramolecular system. The effect of solvent polarity on the stereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. The detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes, which were switched between the ground‐state equilibrium, the relative rate of bond formation in the triplet manifold, as well as deactivation processes between the pro‐(S3) and pro‐(R3) precursors, depending on the temperature domain examined. The enthalpic contribution (ΔΔH≠) was always compensated by the entropic factor (ΔΔS≠), implying the importance of solvation on the diastereo‐differentiation steps. The mechanism of photocycloaddition, especially for the face‐selective processes, is thoroughly discussed, which is supported by quantum chemical calculations on the ground‐state circular dichroism (CD) spectral behavior as well as on the diastereomeric transition states in the triplet excited state.
Poles apart: In an intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether, the effect of solvent polarity on the diastereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. A detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes.</description><subject>1,4-naphthoquinone</subject><subject>asymmetric synthesis</subject><subject>cycloaddition reactions</subject><subject>diastereoselectivity</subject><subject>triplet excited states</subject><subject>vinyl ether</subject><issn>2367-0932</issn><issn>2367-0932</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkE1OwzAQhS0EElXplrUPQMrYsVNniUL5kSqoUGFJ5DgTxSjEJTag7DgCZ-QkNBQBO1bvjfS-WXyEHDKYMgB-bNbBTDmwFDYX3yEjHiezCNKY7_7p-2Ti_cNmwpSQDMSI3J9a7QN26Dw2aIJ9QbqsXXCmN43TZWmDdS29QW2-iqvonW37hs5DjR1d4RBY0uAoOxIfb-9Xel2H2j0929a1eED2Kt14nHznmNyezVfZRbS4Pr_MThaRiaXkkdGQKJaIEmap0EYBq2KhqkIpDjxJGCAIrjAtkqJkVWE4FnqmpDQCpQSM4zGZbv-aznnfYZWvO_uouz5nkA-C8kFQ_iNoA6Rb4NU22P-zzrPlKvtlPwHh92vE</recordid><startdate>201905</startdate><enddate>201905</enddate><creator>Ishikawa, Hiroki</creator><creator>Chung, Tim S.</creator><creator>Fukuhara, Gaku</creator><creator>Shigemitsu, Hajime</creator><creator>Kida, Toshiyuki</creator><creator>Bach, Thorsten</creator><creator>Mori, Tadashi</creator><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-3918-0873</orcidid></search><sort><creationdate>201905</creationdate><title>Diastereoselective Photocycloaddition Reaction of Vinyl Ether Tethered to 1,4‐Naphthoquinone</title><author>Ishikawa, Hiroki ; Chung, Tim S. ; Fukuhara, Gaku ; Shigemitsu, Hajime ; Kida, Toshiyuki ; Bach, Thorsten ; Mori, Tadashi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3552-ca068164d0794ac801f348fb882026610e0428e9b6bd1fbc2eba7855c4e550e33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>1,4-naphthoquinone</topic><topic>asymmetric synthesis</topic><topic>cycloaddition reactions</topic><topic>diastereoselectivity</topic><topic>triplet excited states</topic><topic>vinyl ether</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ishikawa, Hiroki</creatorcontrib><creatorcontrib>Chung, Tim S.</creatorcontrib><creatorcontrib>Fukuhara, Gaku</creatorcontrib><creatorcontrib>Shigemitsu, Hajime</creatorcontrib><creatorcontrib>Kida, Toshiyuki</creatorcontrib><creatorcontrib>Bach, Thorsten</creatorcontrib><creatorcontrib>Mori, Tadashi</creatorcontrib><collection>CrossRef</collection><jtitle>ChemPhotoChem</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ishikawa, Hiroki</au><au>Chung, Tim S.</au><au>Fukuhara, Gaku</au><au>Shigemitsu, Hajime</au><au>Kida, Toshiyuki</au><au>Bach, Thorsten</au><au>Mori, Tadashi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Diastereoselective Photocycloaddition Reaction of Vinyl Ether Tethered to 1,4‐Naphthoquinone</atitle><jtitle>ChemPhotoChem</jtitle><date>2019-05</date><risdate>2019</risdate><volume>3</volume><issue>5</issue><spage>243</spage><epage>250</epage><pages>243-250</pages><issn>2367-0932</issn><eissn>2367-0932</eissn><abstract>The intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether with a small (R)‐point‐chiral group on the tether was studied. Under photoirradiation, [2+2] cyclobutane products were exclusively obtained for this intramolecular system. The effect of solvent polarity on the stereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. The detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes, which were switched between the ground‐state equilibrium, the relative rate of bond formation in the triplet manifold, as well as deactivation processes between the pro‐(S3) and pro‐(R3) precursors, depending on the temperature domain examined. The enthalpic contribution (ΔΔH≠) was always compensated by the entropic factor (ΔΔS≠), implying the importance of solvation on the diastereo‐differentiation steps. The mechanism of photocycloaddition, especially for the face‐selective processes, is thoroughly discussed, which is supported by quantum chemical calculations on the ground‐state circular dichroism (CD) spectral behavior as well as on the diastereomeric transition states in the triplet excited state.
Poles apart: In an intramolecular asymmetric photocycloaddition between 1,4‐naphthoquinone and vinyl ether, the effect of solvent polarity on the diastereoselectivity was significant, with predominant formation of the (2R,S3) over the (2R,R3) isomer in non‐polar solvents being reversed in slightly polar dichloromethane. A detailed temperature‐dependent study revealed the dominant diastereo‐differentiating processes.</abstract><doi>10.1002/cptc.201900022</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0003-3918-0873</orcidid></addata></record> |
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subjects | 1,4-naphthoquinone asymmetric synthesis cycloaddition reactions diastereoselectivity triplet excited states vinyl ether |
title | Diastereoselective Photocycloaddition Reaction of Vinyl Ether Tethered to 1,4‐Naphthoquinone |
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