start-ver=1.4
cd-journal=joma
no-vol=4
cd-vols=
no-issue=1
article-no=
start-page=76
end-page=
dt-received=
dt-revised=
dt-accepted=
dt-pub-year=2021
dt-pub=20210524
dt-online=
en-article=
kn-article=
en-subject=
kn-subject=
en-title=
kn-title=Halogen-sodium exchange enables efficient access to organosodium compounds
en-subtitle=
kn-subtitle=
en-abstract=
kn-abstract=With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used-and are overshadowed by organolithium compounds-because of a lack of convenient and efficient preparation methods. Here we report a halogen-sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking beta-hydrogens, which retards undesired reactions, such as Wurtz-Fittig coupling and beta-hydrogen elimination, and enables efficient halogen-sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents. Halogen-sodium exchange reactions with neopentyl sodium provides access to a range of aryl and alkenyl organosodium compounds in situ, as an alternative to organolithium reagents.
en-copyright=
kn-copyright=

en-aut-name=AsakoSobi
en-aut-sei=Asako
en-aut-mei=Sobi
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=1
ORCID=

en-aut-name=TakahashiIkko
en-aut-sei=Takahashi
en-aut-mei=Ikko
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=2
ORCID=

en-aut-name=NakajimaHirotaka
en-aut-sei=Nakajima
en-aut-mei=Hirotaka
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=3
ORCID=

en-aut-name=IliesLaurean
en-aut-sei=Ilies
en-aut-mei=Laurean
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=4
ORCID=

en-aut-name=TakaiKazuhiko
en-aut-sei=Takai
en-aut-mei=Kazuhiko
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=5
ORCID=

affil-num=1
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=2
en-affil=RIKEN Center for Sustainable Resource Science
kn-affil=

affil-num=3
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=4
en-affil=RIKEN Center for Sustainable Resource Science
kn-affil=

affil-num=5
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=
END

start-ver=1.4
cd-journal=joma
no-vol=141
cd-vols=
no-issue=25
article-no=
start-page=9832
end-page=9836
dt-received=
dt-revised=
dt-accepted=
dt-pub-year=2019
dt-pub=2019611
dt-online=
en-article=
kn-article=
en-subject=
kn-subject=
en-title=
kn-title=Deoxygenative Insertion of Carbonyl Carbon into a C(sp3)–H Bond: Synthesis of Indolines and Indoles
en-subtitle=
kn-subtitle=
en-abstract=
kn-abstract=A simple deoxygenation reagent prepared in situ from commercially available Mo(CO)6 and ortho-quinone has been developed for the synthesis of indoline and indole derivatives. The Mo/quinone complex efficiently deoxygenates carbonyl compounds bearing a neighboring dialkylamino group and effects intramolecular cyclizations with the insertion of a deoxygenated carbonyl carbon into a C(sp3)–H bond, in which a carbonyl group acts as a carbene equivalent. The reaction also proceeds with a catalytic amount of Mo/quinone in the presence of disilane as an oxygen atom acceptor.
en-copyright=
kn-copyright=

en-aut-name=AsakoSobi
en-aut-sei=Asako
en-aut-mei=Sobi
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=1
ORCID=

en-aut-name=IshiharaSeina
en-aut-sei=Ishihara
en-aut-mei=Seina
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=2
ORCID=

en-aut-name=HirataKeiya
en-aut-sei=Hirata
en-aut-mei=Keiya
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=3
ORCID=

en-aut-name=TakaiKazuhiko
en-aut-sei=Takai
en-aut-mei=Kazuhiko
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=4
ORCID=

affil-num=1
en-affil=Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=2
en-affil=Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=3
en-affil=Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=4
en-affil=Graduate School of Natural Science and Technology, Okayama University
kn-affil=
en-keyword=C-H activation
kn-keyword=C-H activation
en-keyword=Oxidative addition
kn-keyword=Oxidative addition
en-keyword=Structural-characterization
kn-keyword=Structural-characterization
en-keyword=Ditungsten hexaalkoxides
kn-keyword=Ditungsten hexaalkoxides
en-keyword=Direct functionalization
kn-keyword=Direct functionalization
en-keyword=Organic-synthesis
kn-keyword=Organic-synthesis
en-keyword=Tertiary-amines
kn-keyword=Tertiary-amines
en-keyword=Oxo-alkylidene
kn-keyword=Oxo-alkylidene
en-keyword=Ketones
kn-keyword=Ketones
en-keyword=Chemistry
kn-keyword=Chemistry
END

start-ver=1.4
cd-journal=joma
no-vol=140
cd-vols=
no-issue=45
article-no=
start-page=15425
end-page=15429
dt-received=
dt-revised=
dt-accepted=
dt-pub-year=2018
dt-pub=20181022
dt-online=
en-article=
kn-article=
en-subject=
kn-subject=
en-title=
kn-title=Use of Cyclopropane as C1 Synthetic Unit by Directed Retro- Cyclopropanation with Ethylene Release
en-subtitle=
kn-subtitle=
en-abstract=
kn-abstract=Cyclopropanation of alkenes is a well-established textbook reaction for the synthesis of cyclopropanes, where a “high-energy” carbene species is exploited to drive the reaction forward. However, little attention has been focused toward molecular transformations involving the reverse reaction, retro-cyclopropanation (RC). This is because of difficulties associated with both cleaving the two geminal C–C single bonds and exploiting the generated carbenes for further transformations in an efficient and selective manner. Here, we report that a molybdenum-based catalytic system overcomes the above challenges and effects the RC of cyclopropanes bearing a pyridyl group with the release of ethylene (alkene) and the subsequent intramolecular cyclization leading to pyrido[2,1-a]isoindoles. The reaction allows for the uncommon use of cyclopropanes as C1 synthetic units in contrast to most conventional reactions in which cyclopropanes are used as C3 synthetic units. We anticipate that this new strategy will pave the way for C1 cyclopropane chemistry.
en-copyright=
kn-copyright=

en-aut-name=SobiAsako
en-aut-sei=Sobi
en-aut-mei=Asako
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=1
ORCID=

en-aut-name= KobashiTakaaki
en-aut-sei= Kobashi
en-aut-mei=Takaaki
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=2
ORCID=

en-aut-name=TakaiKazuhiko
en-aut-sei=Takai
en-aut-mei=Kazuhiko
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=3
ORCID=

affil-num=1
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=2
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=3
en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=
END