Hikaru Yanai

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Organization: Tokyo University of Pharmacy and Life Sciences
Department: School of Pharmacy
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Co-reporter:Hikaru Yanai, Nobuyuki Ishii and Takashi Matsumoto  
Chemical Communications 2016 vol. 52(Issue 51) pp:7974-7977
Publication Date(Web):23 May 2016
DOI:10.1039/C6CC03510H
1,2,3,4-Tetrasubstituted naphthalenes bearing four different substituents were synthesized in a regioselective manner through a fluoride-induced cascade reaction of lactol silyl ethers, which could be easily prepared from 4-alkynylisocoumarins and ketene silyl acetal.
Co-reporter:Hikaru Yanai, Osamu Kobayashi, Kenji Takada, Takuya Isono, Toshifumi Satoh and Takashi Matsumoto  
Chemical Communications 2016 vol. 52(Issue 16) pp:3280-3283
Publication Date(Web):21 Dec 2015
DOI:10.1039/C5CC10115H
In the presence of a strong carbon acid, the sequential Mukaiyama–Michael reaction using two different Michael acceptors proceeded and the reaction of ketene silyl acetal derived from EtOAc with α-pyrones as primal acceptors yielded the corresponding cyclic ketene silyl acetals, which were reactive enough to undergo the following reaction with second acceptors.
Co-reporter:Azusa Sato, Hikaru Yanai, Daiki Suzuki, Midori Okada, Takeo Taguchi
Tetrahedron Letters 2015 Volume 56(Issue 7) pp:925-929
Publication Date(Web):11 February 2015
DOI:10.1016/j.tetlet.2014.12.128
The reaction of difluorohomoallyl alcohols with Me2AlCl in CH2Cl2 selectively gave (Z)-fluoroallyl chlorides via SN2′ type defluorinative chlorination. These chlorides were easily converted to the corresponding (Z)-fluoroallyl azides by the sequential nucleophilic azidation reaction using NaN3. Direct defluorinative azidation of the difluorohomoallyl alcohols was also achieved by treating with Me3SiN3 in the presence of Al(Oi-Pr)3. Fluoroallyl azides thus obtained successfully applied to the Huisgen 1,3-dipolar cycloaddition chemistry.
Co-reporter:Hikaru Yanai, Takeo Taguchi
Journal of Fluorine Chemistry 2015 Volume 174() pp:108-119
Publication Date(Web):June 2015
DOI:10.1016/j.jfluchem.2014.11.006
•(RfSO2)2CH group is strongly acidic CH acid functionality.•Caron acids bearing (RfSO2)2CH group work as potent acid catalysts.•Effective synthesis of carbon acids bearing (RfSO2)2CH is summarized.In this review, we provide an outline of synthetic efforts for carbon acids (CH acids) bearing (RfSO2)2CH group as an acidic functionality. Unlike conventional active methylene compounds such as acetoacetates and malonates are not enough acidic to work as acid catalysts, (RfSO2)2CH-type carbon acids are superacidic in gas phase and catalyze organic reactions in organic solvents.
Co-reporter:Dr. Hikaru Yanai;Saki Egawa;Kenta Yamada;Junpei Ono;Dr. Motohide Aoki;Dr. Takashi Matsumoto;Dr. Takeo Taguchi
Asian Journal of Organic Chemistry 2014 Volume 3( Issue 4) pp:556-563
Publication Date(Web):
DOI:10.1002/ajoc.201402010

Abstract

1,1-Bis(triflyl)alkadienes are easily prepared by mixing bis(triflyl)methane and α,β-unsaturated aldehydes and then used as easy-to-handle building blocks for the preparation of strongly acidic carbon acids. The reaction of these alkadienes with either NaBH4 or organocerium reagents gave the desired carbon acids through a β-selective nucleophilic addition reaction. Similar reactions of a 1,1-bis(trifyl)alkadiene with sterically bulky iPrMgBr resulted in a δ-selective alkylation instead. The present β-alkylation is the realization of the synthesis of β-branched 1,1-bis(triflyl)alkanes with an acidic CH moiety. Furthermore, when submitted to a Mukaiyama aldol reaction, such β-branched carbon acids had a higher catalyst activity than that of the corresponding nonbranched carbon acids.

Co-reporter:Hikaru Yanai, Yoichi Takahashi, Haruhiko Fukaya, Yasuo Dobashi and Takashi Matsumoto  
Chemical Communications 2013 vol. 49(Issue 86) pp:10091-10093
Publication Date(Web):05 Sep 2013
DOI:10.1039/C3CC46171H
Stable and easy-to-handle zwitterions containing carbanion and pyridinium moieties were synthesized, and their structural studies by both X-ray crystallography and theoretical methods revealed the stereoelectronic effect in the zwitterionic ‘C−–C–N+’ system.
Co-reporter:Dr. Hikaru Yanai;Nobuyuki Ishii;Dr. Takashi Matsumoto;Dr. Takeo Taguchi
Asian Journal of Organic Chemistry 2013 Volume 2( Issue 11) pp:989-996
Publication Date(Web):
DOI:10.1002/ajoc.201300157

Abstract

By choosing the organic acid catalysts, the reaction of lactones with ketene silyl acetals results in selective formation of simple Mukaiyama aldol adducts or olefination products, which are formed by the subsequent elimination of a silanol from the adducts. That is, in the presence of acidic zwitterions, the reaction of lactones with ketene silyl acetals gives simple Mukaiyama aldol adducts in excellent yields. In contrast, the same reaction in the presence of a carbon acid catalyst brings about the formation of olefination products in a Z-selective manner.

Co-reporter:Hikaru Yanai, Saki Egawa, Takeo Taguchi
Tetrahedron Letters 2013 Volume 54(Issue 17) pp:2160-2163
Publication Date(Web):24 April 2013
DOI:10.1016/j.tetlet.2013.02.039
A convenient and practical synthesis of 1,1-bis(triflyl)alkenes via self-promoting condensation of Tf2CH2 and aldehydes was developed and chemical behavior of these alkenes was investigated. Among the alkenes, easily isolable 1,1-bis(triflyl)alkadienes derived from α,β-unsaturated aldehydes could be used as useful building blocks for 1,1-bis(triflyl)alkanes. The 1,1-bis(triflyl)alkane thus obtained showed catalyst activity in the acetal forming reaction, which is a typical reaction catalyzed by Brønsted acids.
Co-reporter:Dr. Hikaru Yanai;Tasuku Yoshino;Masaya Fujita;Haruhiko Fukaya;Dr. Akira Kotani;Dr. Fumiyo Kusu ;Dr. Takeo Taguchi
Angewandte Chemie 2013 Volume 125( Issue 5) pp:1600-1603
Publication Date(Web):
DOI:10.1002/ange.201208809
Co-reporter:Dr. Hikaru Yanai;Tasuku Yoshino;Masaya Fujita;Haruhiko Fukaya;Dr. Akira Kotani;Dr. Fumiyo Kusu ;Dr. Takeo Taguchi
Angewandte Chemie International Edition 2013 Volume 52( Issue 5) pp:1560-1563
Publication Date(Web):
DOI:10.1002/anie.201208809
Co-reporter:Hikaru Yanai and Takeo Taguchi  
Chemical Communications 2012 vol. 48(Issue 71) pp:8967-8969
Publication Date(Web):18 Jul 2012
DOI:10.1039/C2CC33606E
(Z)-Selective olefination of several lactones with ketene silyl acetals was achieved by the catalysis of carbon acids (C–H acids) having a bis(triflyl)methyl group as an acidic functionality; in particular, the triple carbon acid having three bis(triflyl)methyl groups in phloroglucinol shows an excellent catalytic performance.
Co-reporter:Akio Saito, Manabu Tojo, Hikaru Yanai, Fukiko Wada, Muga Nakagawa, Midori Okada, Azusa Sato, Rieko Okatani, Takeo Taguchi
Journal of Fluorine Chemistry 2012 Volume 133() pp:38-51
Publication Date(Web):January 2012
DOI:10.1016/j.jfluchem.2011.07.022
CrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl2/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.Graphical abstractCrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters provided 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.Highlights► Efficient synthesis of (Z)-1-fluoro-1-alkenyl carboxylates, carbonates and carbamates. ► CrCl2/Mn-mediated transformation of dibromofluorocarbinyl esters via chromium fluorocarbene complex. ► Stepwise double acyl transfer reaction of 1-fluoro-1-alkenyl esters with nucleophies including bifunctional nucleopile such as ethylene diamine derivative.
Co-reporter:Hikaru Yanai, Takuji Sakiyama, Tomoko Oguchi, Takeo Taguchi
Tetrahedron Letters 2012 Volume 53(Issue 25) pp:3161-3164
Publication Date(Web):20 June 2012
DOI:10.1016/j.tetlet.2012.04.046
In the presence of catalytic amount of indium(III) Lewis acids, the four component reaction of aldehydes, isocyanides, trimethylsilyl azide and aliphatic alcohols smoothly proceeded to give alkoxylated 1H-tetrazole products in good yields. In particular, In(OTf)3 and In(ONf)3 showed notably high level of catalytic activity in this reaction.
Co-reporter:Daisuke Watanabe, Minoru Koura, Akio Saito, Hikaru Yanai, Yuko Nakamura, Midori Okada, Azusa Sato, Takeo Taguchi
Journal of Fluorine Chemistry 2011 Volume 132(Issue 5) pp:327-338
Publication Date(Web):May 2011
DOI:10.1016/j.jfluchem.2011.03.007
Difluoroallylation of optically pure O-silylated (S)-2-methyl-3-hydroxypropanal 10a with bromodifluoropropene mediated by indium provided the corresponding difluorohomoallyl alcohol 11a with low diastereoselectivity, but without a decrease in optical purity. Defluorinative allylic alkylation of each diastereomer of the difluorohomoallyl alcohol efficiently proceeded by the reaction with trialkylaluminium and Cu(I) system or Grignard reagent and a catalytic amount of CuI system in THF to give the fluorine-substituted allylic alcohol 12 in an high yield and in an excellent Z selective manner. Subsequent imidate Claisen rearrangement of the allylic alcohol 12 proceeded with a complete 1,3-chirality transfer to give the fluoroalkene dipeptide isostere structure 14 after the final conversion of the primary alcohol 20 into the carboxylic acid form.Graphical abstractHighlights► High yield and highly Z selective allylic alkylation reaction of difluorohomoally alcohol derivatives with Grignard reagents and CuI catalyst leading to fluoroallyl alcohol derivatives. ► Complete 1,3-chirality transfer in the imidate Claisen rearrangement of the above fluoroallyl alcohol derivatives. ► A convienient method for the preparation of (Z)-fluoroalkene dipeptide isosteres in optically pure form.
Co-reporter:Hikaru Yanai, Nobuyuki Ishii and Takashi Matsumoto
Chemical Communications 2016 - vol. 52(Issue 51) pp:NaN7977-7977
Publication Date(Web):2016/05/23
DOI:10.1039/C6CC03510H
1,2,3,4-Tetrasubstituted naphthalenes bearing four different substituents were synthesized in a regioselective manner through a fluoride-induced cascade reaction of lactol silyl ethers, which could be easily prepared from 4-alkynylisocoumarins and ketene silyl acetal.
Co-reporter:Hikaru Yanai and Takeo Taguchi
Chemical Communications 2012 - vol. 48(Issue 71) pp:NaN8969-8969
Publication Date(Web):2012/07/18
DOI:10.1039/C2CC33606E
(Z)-Selective olefination of several lactones with ketene silyl acetals was achieved by the catalysis of carbon acids (C–H acids) having a bis(triflyl)methyl group as an acidic functionality; in particular, the triple carbon acid having three bis(triflyl)methyl groups in phloroglucinol shows an excellent catalytic performance.
Co-reporter:Hikaru Yanai, Osamu Kobayashi, Kenji Takada, Takuya Isono, Toshifumi Satoh and Takashi Matsumoto
Chemical Communications 2016 - vol. 52(Issue 16) pp:NaN3283-3283
Publication Date(Web):2015/12/21
DOI:10.1039/C5CC10115H
In the presence of a strong carbon acid, the sequential Mukaiyama–Michael reaction using two different Michael acceptors proceeded and the reaction of ketene silyl acetal derived from EtOAc with α-pyrones as primal acceptors yielded the corresponding cyclic ketene silyl acetals, which were reactive enough to undergo the following reaction with second acceptors.
Co-reporter:Hikaru Yanai, Yoichi Takahashi, Haruhiko Fukaya, Yasuo Dobashi and Takashi Matsumoto
Chemical Communications 2013 - vol. 49(Issue 86) pp:NaN10093-10093
Publication Date(Web):2013/09/05
DOI:10.1039/C3CC46171H
Stable and easy-to-handle zwitterions containing carbanion and pyridinium moieties were synthesized, and their structural studies by both X-ray crystallography and theoretical methods revealed the stereoelectronic effect in the zwitterionic ‘C−–C–N+’ system.
1,4,7-trihydroxy-8-(3-methyl-2-butenyl)-9H-xanthen-9-one
2-OXAZOLIDINONE, 3-[(METHYLTHIO)ACETYL]-4-(PHENYLMETHYL)-, (4R)-
Magnesium, chloro(2-methyl-1-propenyl)-
Phosphine oxide, (1-methoxyethyl)diphenyl-
Silane, [(1-methoxy-2-methyl-1-propenyl)oxy]tris(1-methylethyl)-
2-Hexanone, 5,5-dimethoxy-
PENTANAMIDE, N,4,4-TRIMETHOXY-N-METHYL-
2H-Pyran-2-one, 5-iodo-6-phenyl-
1H-2-Benzopyran-1-one, 3-phenyl-4-(phenylethynyl)-
Silane, (1,1-dimethylethyl)[(1-ethoxy-2-methyl-1-propenyl)oxy]dimethyl-