start-ver=1.4 cd-journal=joma no-vol= cd-vols= no-issue= article-no= start-page=1 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2021 dt-pub=2021 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Chromium carbides and cyclopropenylidenes en-subtitle= kn-subtitle= en-abstract= kn-abstract=Carbon tetrabromide can be reduced with CrBr2 in THF to form a dinuclear carbido complex, [CrBr2(thf)(2))][CrBr2(thf)(3)](mu-C), along with formation of [CrBr3(thf)(3)]. An X-ray diffraction (XRD) study of the pyridine adduct displayed a dinuclear structure bridged by a carbido ligand between 5- and 6-coordinate chromium centers. The carbido complex reacted with two equivalents of aldehydes to form alpha,beta-unsaturated ketones. Treatment of the carbido complex with alkenes resulted in a formal double-cyclopropanation of alkenes by the carbido moiety to afford spiropentanes. Isotope labeling studies using a C-13-enriched carbido complex, [CrBr2(thf)(2))][CrBr2(thf)(3)](mu-C-13), identified that the quaternary carbon in the spiropentane framework was delivered by carbide transfer from the carbido complex. Terminal and internal alkynes also reacted with the carbido complex to form cyclopropenylidene complexes. A solid-state structure of the diethylcyclopropenylidene complex, prepared from 3-hexyne, showed a mononuclear cyclopropenylidene chromium(iii) structure. en-copyright= kn-copyright= en-aut-name=KurogiTakashi en-aut-sei=Kurogi en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=IrifuneKeiichi en-aut-sei=Irifune en-aut-mei=Keiichi 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 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=12 cd-vols= no-issue=10 article-no= start-page=3509 end-page=3515 dt-received= dt-revised= dt-accepted= dt-pub-year=2021 dt-pub=20210119 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear titanium(iii) methylene complex en-subtitle= kn-subtitle= en-abstract= kn-abstract=Transmetallation of a zinc methylene complex [ZnI(tmeda)](2)(mu-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. The X-ray diffraction study displayed a dinuclear methylene structure [TiCl(tmeda)](2)(mu-CH2)(mu-Cl)(2). Treatment of an ester with the titanium methylene complex resulted in methylenation of the ester carbonyl to form a vinyl ether. The titanium methylene complex also reacted with a terminal olefin, resulting in olefin-metathesis and olefin-homologation. Cyclopropanation by methylene transfer from the titanium methylene proceeded by use of a 1,3-diene. The mechanistic study of the cyclopropanation reaction by the density functional theory calculations was also reported. en-copyright= kn-copyright= en-aut-name=KurogiTakashi en-aut-sei=Kurogi en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KurokiKaito en-aut-sei=Kuroki en-aut-mei=Kaito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MoritaniShunsuke en-aut-sei=Moritani en-aut-mei=Shunsuke 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=Division of Applied Chemistry, Graduate School of National Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of National Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of National Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of National 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=21 cd-vols= no-issue=17 article-no= start-page=6756 end-page=6760 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190808 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Rhenium-Catalyzed Cyclization via 1,2-Iodine and 1,5-Hydrogen Migration for the Synthesis of 2-Iodo-1H-indenes en-subtitle= kn-subtitle= en-abstract= kn-abstract=A rhenium complex catalyzed the formation of 2-iodo-1H-indene derivatives through iodine and hydrogen migration of 3-iodopropargyl ethers. The reaction proceeded via generation of 1-iodoalkenylrhenium carbene species by sequential 1,2-iodine and 1,5-hydrogen shifts with readily available precursors under neutral conditions. The reaction mechanism and the reactivity of the generated alkenylcarbene species were also investigated. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 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=2 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= en-keyword=anti-markovnikov addition kn-keyword=anti-markovnikov addition en-keyword=silyl enol ethers kn-keyword=silyl enol ethers en-keyword=terminal alkynes kn-keyword=terminal alkynes en-keyword=metal vinylidenes kn-keyword=metal vinylidenes en-keyword=cycloisomerization kn-keyword=cycloisomerization en-keyword=ruthenium kn-keyword=ruthenium en-keyword=complexes kn-keyword=complexes en-keyword=derivatives kn-keyword=derivatives en-keyword=carbene kn-keyword=carbene en-keyword=functionalization kn-keyword=functionalization END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=9 article-no= start-page=3441 end-page=3445 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190418 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Rhenium-Catalyzed Regioselective ortho-Alkenylation and [3 + 2 + 1] Cycloaddition of Phenols with Internal Alkynes en-subtitle= kn-subtitle= en-abstract= kn-abstract=An operationally simple and direct rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes was developed. The protocol provided ortho-alkenylphenols exclusively, and formation of para- or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products were not observed. The [3 + 2 + 1] cycloaddition of phenols and two alkynes via ortho-alkenylation was also demonstrated, in which the alkynes functioned as both two- and one-carbon units. These reactions proceeded with readily available starting materials under neutral conditions without additional ligands. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=YamamotoMasaki en-aut-sei=Yamamoto en-aut-mei=Masaki 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=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= en-keyword=anti-markovnikov addition kn-keyword=anti-markovnikov addition en-keyword=intramolecular hydroarylation kn-keyword=intramolecular hydroarylation en-keyword=oxidative annulation kn-keyword=oxidative annulation en-keyword=gold kn-keyword=gold en-keyword=hydrophenoxylation kn-keyword=hydrophenoxylation en-keyword=construction kn-keyword=construction en-keyword=cyclization kn-keyword=cyclization en-keyword=vinylation kn-keyword=vinylation en-keyword=alkenes kn-keyword=alkenes END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=8 article-no= start-page=2668 end-page=2672 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190404 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Chromium-Mediated Stannylcyclopropanation of Alkenes with (Diiodomethyl)stannanes en-subtitle= kn-subtitle= en-abstract= kn-abstract=A stannyl-group-substituted gem-dichromiomethane species, generated in situ from CrCl2, TMEDA, and tributyl(diiodomethyl)stannane, worked as an efficient stannylcarbene equivalent to promote cyclopropanation of alkenes. The reaction provided synthetically useful stannylcyclopropanes directly from commercially available unactivated alkenes without using potentially flammable alkylzinc and diazo compounds. Structural characterization of stannyl- and germyl-group-substituted gem-dichromiomethane complexes and the effect of group 14 elements containing substituents for cyclopropanation are also described. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TaniguchiRyuji en-aut-sei=Taniguchi en-aut-mei=Ryuji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MizutaChisato en-aut-sei=Mizuta en-aut-mei=Chisato 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=chromium(II)-mediate synthesis kn-keyword=chromium(II)-mediate synthesis en-keyword=stereoselective-synthesis kn-keyword=stereoselective-synthesis en-keyword=e-alkenylstannanes kn-keyword=e-alkenylstannanes en-keyword=redox system kn-keyword=redox system en-keyword=cyclopropanation kn-keyword=cyclopropanation en-keyword=aldehydes kn-keyword=aldehydes en-keyword=reagents kn-keyword=reagents en-keyword=cyclopropenes kn-keyword=cyclopropenes en-keyword=reactivity kn-keyword=reactivity en-keyword=reduction kn-keyword=reduction END start-ver=1.4 cd-journal=joma no-vol=25 cd-vols= no-issue=66 article-no= start-page=15189 end-page=15197 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190918 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Mechanistic Insights into Rhenium-Catalyzed Regioselective C-Alkenylation of Phenols with Internal Alkynes en-subtitle= kn-subtitle= en-abstract= kn-abstract= A (ƒĘ-aryloxo)rhenium complex was isolated and confirmed as a key precatalyst for rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes. The reaction exclusively provided ortho-alkenylphenols; the formation of para or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products was not observed. Several mechanistic experiments excluded a classical Friedel-Crafts-type mechanism, leading to the proposed phenolic hydroxyl group assisted electrophilic alkenylation as the most plausible reaction mechanism. For this purpose, the use of rhenium, a metal between the early and late transition metals in the periodic table, was key for the activation of both the soft carbon-carbon triple bond of the alkyne and the hard oxygen atom of the phenol, at the same time. ortho-Selective alkenylation with allenes also provided the corresponding adducts with a substitution pattern different from that obtained by the addition reaction with alkynes. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=YamamotoMasaki en-aut-sei=Yamamoto en-aut-mei=Masaki 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= en-keyword=alkenylation kn-keyword=alkenylation en-keyword=homogeneous catalysis kn-keyword=homogeneous catalysis en-keyword=reaction mechanisms kn-keyword=reaction mechanisms en-keyword=regioselectivity kn-keyword=regioselectivity en-keyword=rhenium kn-keyword=rhenium 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 ghigh-energyh 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 start-ver=1.4 cd-journal=joma no-vol=8 cd-vols= no-issue=6 article-no= start-page=5454 end-page=5459 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20180504 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Amine-Promoted anti-Markovnikov Addition of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis en-subtitle= kn-subtitle= en-abstract= kn-abstract=Amines have been identified to greatly accelerate the intermolecular anti-Markovnikov addition of carbon nucleophiles to unactivated terminal alkynes. Using a combination of [ReBr(CO)3(thf)]2 and iPr2NEt, construction of cyclic all-carbon quaternary centers was achieved with various 1,3-ketoesters, diketones, and diesters with lower catalyst loading under milder conditions. The type of addition could be easily controlled by choice of additive, highlighting the unique features of rhenium catalysis en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=UemuraErika en-aut-sei=Uemura en-aut-mei=Erika 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 and Biochemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=rhenium kn-keyword=rhenium en-keyword=anti-Markovnikov addition kn-keyword=anti-Markovnikov addition en-keyword=1,3-dicarbonyl compound kn-keyword=1,3-dicarbonyl compound en-keyword=vinylidene kn-keyword=vinylidene en-keyword=amine kn-keyword=amine END start-ver=1.4 cd-journal=joma no-vol=18 cd-vols= no-issue=17 article-no= start-page=4380 end-page=4383 dt-received= dt-revised= dt-accepted= dt-pub-year=2016 dt-pub=20160811 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis and Properties of Sila[n]helicenes via Dehydrogenative Silylation of C-H Bonds under Rhodium Catalysis en-subtitle= kn-subtitle= en-abstract= kn-abstract= Use of a rhodium catalyst with (R)-(S)-BPPFA ligand allows efficient synthesis of sila[n]helicenes via dehydrogenative silylation of C-H bonds. By selecting the proper ligands, the current method provides the ability to prepare unsymmetrical sila[n]helicene derivatives without any oxidants. The resulting sila[6]helicene is a rare example of a five-membered ring-fused [6]helicene, which was isolated as a single pure enantiomer without substituents on the terminal benzene rings. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=OkadaRyo en-aut-sei=Okada en-aut-mei=Ryo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NishiyamaAtsushi en-aut-sei=Nishiyama en-aut-mei=Atsushi 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=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= affil-num=4 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=696 cd-vols= no-issue=1 article-no= start-page=348 end-page=351 dt-received= dt-revised= dt-accepted= dt-pub-year=2011 dt-pub=20110101 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Rhenium-catalyzed insertion of terminal alkenes into a C(sp(2))?H bond and successive transfer hydrogenation en-subtitle= kn-subtitle= en-abstract= kn-abstract=Treatment of aromatic aldimines with terminal alkenes in the presence of a rhenium catalyst, [HRe(CO)(4)](n), gives 2-alkenylbenzylamines in good to excellent yields. This reaction proceeds via the insertion of the alkene into a C-H bond at the ortho-position of the imino group of the aromatic aldimine followed by sequential beta-hydride elimination from the formed alkyl rhenium intermediate and then by hydrogenation of the imino group of the aldimine. en-copyright= kn-copyright= en-aut-name=KuninobuYoichiro en-aut-sei=Kuninobu en-aut-mei=Yoichiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=NakaharaTakahiro en-aut-sei=Nakahara en-aut-mei=Takahiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=YuPeng en-aut-sei=Yu en-aut-mei=Peng 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= kn-affil=Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University affil-num=2 en-affil= kn-affil=Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University affil-num=3 en-affil= kn-affil=Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University affil-num=4 en-affil= kn-affil=Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University en-keyword=Rhenium kn-keyword=Rhenium en-keyword=Insertion kn-keyword=Insertion en-keyword=Hydrogen transfer kn-keyword=Hydrogen transfer en-keyword=Aldimine kn-keyword=Aldimine en-keyword=Alkene kn-keyword=Alkene END