Jun-ichi Matsuo

Name:

Organization: Kanazawa University

Department: Institute of Medical

Title:

Chemicals
References

Synthesis of multisubstituted phenols by formal [4 + 2] cycloaddition of nucleophilic alkynes with 3-ethoxycyclobutanones

Co-reporter:Takeo Kuzuguchi;Yuto Yabuuchi;Tomoyuki Yoshimura

Organic & Biomolecular Chemistry 2017 vol. 15(Issue 25) pp:5268-5271

Publication Date(Web):2017/06/27

DOI:10.1039/C7OB00827A

Nucleophilic alkynes bearing sulfonamide, trimethylsilyl, or p-methoxyphenyl groups at the sp carbon reacted with 3-ethoxycyclobutanones to give formal [4 + 2] cycloadducts by activation with TiCl4. Reactions with 2-monoalkyl and 2-nonsubstituted 3-ethoxycyclobutanones gave phenol derivatives directly by benzannulation, while the use of 2,2-dimethyl-3-ethoxycyclobutanone gave the corresponding dienones, which were converted to pentasubstituted phenols by dienone-phenol rearrangement. Regioselectivity that depended on the activation conditions of dienone-phenol rearrangement is also described.

Synthesis of α-Halo-γ-hydroxyenamides by Titanium Tetrahalide Mediated Addition of Aldehydes or Ketones to Ynamides

Co-reporter:Yuto Yabuuchi, Takeo Kuzuguchi, Tomoyuki Yoshimura, and Jun-ichi Matsuo

Organic Letters 2016 Volume 18(Issue 19) pp:4951-4953

Publication Date(Web):September 20, 2016

DOI:10.1021/acs.orglett.6b02526

α-Chloro- or α-bromo-γ-hydroxyenamides were synthesized by the reaction of an ynamide, titanium tetrahalide, and an aldehyde or a ketone. A γ-hydroxy trisubstituted enamide was prepared stereoselectively by Suzuki coupling of an obtained α-chloro-γ-hydroxyenamide with phenyl boronic acid. Intramolecular cyclization of α-chloro-γ-hydroxyenamide took place to provide a 2,3-dihydrobenzoisothiazole 1,1-dioxide derivative by palladium-catalyzed C–H activation of the tosyl group. Hydrochlorination of ynamides proceeded to give α-chloroenamides by treatment with titanium tetrachloride followed by addition of water.

1,4-Zwitterionic intermediates formed by cleavage of a cyclobutane ring and their cycloaddition reactions

Co-reporter:Jun-ichi Matsuo

Tetrahedron Letters 2014 Volume 55(Issue 16) pp:2589-2595

Publication Date(Web):16 April 2014

DOI:10.1016/j.tetlet.2014.03.053

Cycloaddition reaction is an efficient organic reaction because all of the substrate components are introduced into a product skeleton. Recently, more than six-membered rings have been synthesized by Lewis acid-promoted ring cleavage of a cyclobutane ring followed by addition to an unsaturated bond. Typical examples in the literature of these types of reactions using 1-donor–2-acceptor cyclobutanes and 3-donor cyclobutanones with Lewis acids are presented in this Letter.Figure optionsDownload full-size imageDownload as PowerPoint slide

Chemoselective Formal [4+2] Cycloaddition of 3-Hydroxycyclobutanones with Enones

Co-reporter:Kosuke Harada;Aya Nowaki ;Dr. Jun-ichi Matsuo

Asian Journal of Organic Chemistry 2013 Volume 2( Issue 11) pp:923-926

Publication Date(Web):

DOI:10.1002/ajoc.201300156

40 Jahre Mukaiyama-Aldolreaktion: eine Erfolgsgeschichte

Co-reporter:Dr. Jun-ichi Matsuo;Dr. Masahiro Murakami

Angewandte Chemie 2013 Volume 125( Issue 35) pp:9280-9289

Publication Date(Web):

DOI:10.1002/ange.201303192

Abstract

Die Mukaiyama-Aldolreaktion, über die Teruaki Mukaiyama 1973 erstmals berichtete, ist eine gerichtete gekreuzte Aldolreaktion von Silylenolethern mit Carbonylverbindungen in Gegenwart einer Lewis-Säure. Varianten dieser Reaktion, die ebenfalls in der Arbeitsgruppe Mukaiyama entwickelt wurden, sind die gerichteten gekreuzten Aldolreaktionen in Gegenwart von Borenolaten und Zinn(II)-enolaten. Allesamt sind es wertvolle Methoden für den Aufbau von stereochemisch komplexen Molekülen aus zwei Carbonylverbindungen. Dieser Kurzaufsatz gibt einen historischen Überblick über die Entdeckung und frühe Entwicklungsphase dieser Reaktionen.

Regioselective Inter- and Intramolecular Formal [4+2] Cycloaddition of Cyclobutanones with Indoles and Total Synthesis of ()-Aspidospermidine

Co-reporter:Mizuki Kawano;Takaaki Kiuchi;Shoko Negishi;Hiroyuki Tanaka;Takaya Hoshikawa;Dr. Jun-ichi Matsuo;Dr. Hiroyuki Ishibashi

Angewandte Chemie 2013 Volume 125( Issue 3) pp:940-944

Publication Date(Web):

DOI:10.1002/ange.201206734

The Mukaiyama Aldol Reaction: 40Years of Continuous Development

Co-reporter:Dr. Jun-ichi Matsuo;Dr. Masahiro Murakami

Angewandte Chemie International Edition 2013 Volume 52( Issue 35) pp:9109-9118

Publication Date(Web):

DOI:10.1002/anie.201303192

Abstract

A directed cross-aldol reaction of silyl enol ethers with carbonyl compounds, such as aldehydes and ketones, promoted by a Lewis acid, a reaction which is now widely known as the Mukaiyama aldol reaction. It was first reported in 1973, and this year marks the 40th anniversary. The directed cross-aldol reactions mediated by boron enolates and tin(II) enolates also emerged from the Mukaiyama laboratory. These directed cross-aldol reactions have become invaluable tools for the construction of stereochemically complex molecules from two carbonyl compounds. This Minireview provides a succinct historical overview of their discoveries and the early stages of their development.

Regioselective Inter- and Intramolecular Formal [4+2] Cycloaddition of Cyclobutanones with Indoles and Total Synthesis of ()-Aspidospermidine

Co-reporter:Mizuki Kawano;Takaaki Kiuchi;Shoko Negishi;Hiroyuki Tanaka;Takaya Hoshikawa;Dr. Jun-ichi Matsuo;Dr. Hiroyuki Ishibashi

Angewandte Chemie International Edition 2013 Volume 52( Issue 3) pp:906-910

Publication Date(Web):

DOI:10.1002/anie.201206734

Formal [4+2] cycloaddition of cyclobutanones bearing alkyne–cobalt complex at their 3-positions

Co-reporter:Mizuki Kawano, Takaaki Kiuchi, Jun-ichi Matsuo, Hiroyuki Ishibashi

Tetrahedron Letters 2012 Volume 53(Issue 4) pp:432-434

Publication Date(Web):25 January 2012

DOI:10.1016/j.tetlet.2011.11.067

Cyclobutanones bearing an alkyne–cobalt complex at their 3-positions reacted with aldehydes to give formal [4+2] cycloadducts by using tin(IV) chloride as a Lewis acid. Highly substituted tetrahydropyrone derivatives were stereoselectively prepared by this method.

Indium(III) triflate-catalyzed reaction of 2-carbomethoxycyclobutanone with nitrones

Co-reporter:Jun-ichi Matsuo, Ryosuke Okuno, Hiroyuki Ishibashi

Tetrahedron Letters 2012 Volume 53(Issue 17) pp:2257-2259

Publication Date(Web):25 April 2012

DOI:10.1016/j.tetlet.2012.02.092

2-Carbomethoxycyclobutanone reacted with N-phenyl-C-arylnitrones to afford methyl 5-oxo-2-[aryl(phenylamino)methyl]tetrahydrofuran-2-carboxylates by the catalysis of indium(III) triflate in the presence of magnesium sulfate.

Brønsted Acid Catalyzed Asymmetric Reduction of Ketones and Acyl Silanes Using Chiral anti-Pentane-2,4-diol

Co-reporter:Jun-ichi Matsuo, Yu Hattori and Hiroyuki Ishibashi

Organic Letters 2010 Volume 12(Issue 10) pp:2294-2297

Publication Date(Web):April 22, 2010

DOI:10.1021/ol1006532

Ketones and acyl silanes were reduced to the corresponding alcohols by a simple procedure employing anti-1,3-diol and a catalytic amount (5 mol %) of 2,4-dinitrobenzenesulfonic acid in benzene at reflux. Asymmetric induction reached up to >99% ee when a chiral pentane-2,4-diol of 97% ee was used.

Titanium(IV) Chloride-Mediated Carbon−Carbon Bond-Forming Reaction between 3,3-Dialkylcyclobutanones and Aldehydes

Co-reporter:Jun-ichi Matsuo, Mizuki Kawano, Ryosuke Okuno and Hiroyuki Ishibashi

Organic Letters 2010 Volume 12(Issue 17) pp:3960-3962

Publication Date(Web):August 6, 2010

DOI:10.1021/ol101653b

Treatment of 3,3-dialkylcyclobutanones with titanium(IV) chloride in the presence of aldehyde gave β′-chloro-β-hydroxy ketones in high yields. It was speculated that ring cleavage of the cyclobutanone ring with titanium(IV) chloride gave trichlorotitanium enolate having a tertiary alkyl chloride moiety and then aldol reaction of the titanium enolate proceeded. A trialkylsilylmethyl group at the 2-position of cyclobutanone facilitated the ring cleavage. Synthesis of substituted cyclopentenone from an obtained product is also described.

Asymmetric Synthesis of 2,3-Dihydro-4-pyranones by Reaction of Chiral 3-Alkoxycyclobutanone and Aldehydes

Co-reporter:Shoko Negishi, Hiroyuki Ishibashi, and Jun-ichi Matsuo

Organic Letters 2010 Volume 12(Issue 21) pp:4984-4987

Publication Date(Web):October 5, 2010

DOI:10.1021/ol1021355

Chiral cyclobutanone which had ethyl l-lactate as a chiral auxiliary at the 3-position reacted with aldehydes to give 2,3-dihydro-4-pyranones in up to 93% ee by combined use of titanium(IV) chloride and tin(II) chloride.

A New Synthesis of 2,3-Di- or 2,3,3-Trisubstituted 2,3-Dihydro-4-pyridones by Reaction of 3-Ethoxycyclobutanones and N-p-Toluenesulfonyl Imines Using Titanium(IV) Chloride: Synthesis of (±)-Bremazocine

Co-reporter:Jun-ichi Matsuo, Ryohei Okado and Hiroyuki Ishibashi

Organic Letters 2010 Volume 12(Issue 14) pp:3266-3268

Publication Date(Web):June 22, 2010

DOI:10.1021/ol1012313

N-p-Toluenesulfonyl (Ts) aldimines reacted with 3-ethoxycyclobutanones by catalysis of titanium(IV) chloride to afford 2,3-di- or 2,3,3-trisubstituted N-Ts-2,3-dihydro-4-pyridones. Synthesis of (±)-bremazocine was efficiently accomplished by using this method.

Intramolecular formal [4+2] cycloaddition of 3-ethoxycyclobutanones and alkenes

Co-reporter:Jun-ichi Matsuo, Shun Sasaki, Takaya Hoshikawa and Hiroyuki Ishibashi

Chemical Communications 2010 vol. 46(Issue 6) pp:934-936

Publication Date(Web):06 Jan 2010

DOI:10.1039/B919332D

Intramolecular formal [4+2] cycloaddition between 3-ethoxycyclobutanones and a carbon–carbon double bond to the corresponding bicyclo[4.n.0]alkan-2-one derivatives proceeded effectively by using ethylaluminium dichloride.

An efficient procedure for preparation of 2-monoalkyl or 2-monoaryl-3-ethoxycyclobutanones

Co-reporter:Jun-ichi Matsuo, Ryosuke Okuno, Kosuke Takeuchi, Mizuki Kawano, Hiroyuki Ishibashi

Tetrahedron Letters 2010 Volume 51(Issue 29) pp:3736-3737

Publication Date(Web):21 July 2010

DOI:10.1016/j.tetlet.2010.05.031

Optimized reaction conditions for the preparation of various 2-monosubstituted 3-ethoxycyclobutanones are described. 2-Monoalkyl 3-ethoxycyclobutanones were efficiently prepared by the reaction of the corresponding carboxylic acid chlorides and an excess amount of ethyl vinyl ether in the presence of diisopropylethylamine at 90 °C in a sealed tube. 2-Monoaryl 3-ethoxycyclobutanones were prepared by using 2,6-lutidine as a base in the above-mentioned procedure..

Asymmetric reduction of aliphatic ketones and acyl silanes using chiral anti-pentane-2,4-diol and a catalytic amount of 2,4-dinitrobenzenesulfonic acid

Co-reporter:Jun-ichi Matsuo, Yu Hattori, Mio Hashizume, Hiroyuki Ishibashi

Tetrahedron 2010 66(32) pp: 6062-6069

Publication Date(Web):

DOI:10.1016/j.tet.2010.06.012

Tin(IV) Chloride Catalyzed Cycloaddition Reactions between 3-Ethoxycyclobutanones and Allylsilanes

Co-reporter:Jun-ichi Matsuo, Shun Sasaki, Takaya Hoshikawa and Hiroyuki Ishibashi

Organic Letters 2009 Volume 11(Issue 17) pp:3822-3825

Publication Date(Web):July 30, 2009

DOI:10.1021/ol901329c

Formal [4 + 2] cycloaddition between various 3-ethoxycyclobutanones and allyltrialkylsilanes proceeded to give 3-ethoxy-5-[(trialkylsilyl)methyl]cyclohexan-1-ones by catalysis with tin(VI) chloride. The use of allyl-tert-butyldiphenylsilane induced 1,5-hydride transfer, which gave 2-[3-(tert-butyldiphenylsilyl)propyl]-6-methyltetrahydro-4-pyrones.

Formal [4+2] cycloaddition between 3-ethoxycyclobutanones and silyl enol ethers

Co-reporter:Jun-ichi Matsuo, Shoko Negishi, Hiroyuki Ishibashi

Tetrahedron Letters 2009 50(42) pp: 5831-5833

Publication Date(Web):

DOI:10.1016/j.tetlet.2009.08.013

Asymmetric synthesis of 2-alkyl-4-hydroxycyclohex-2-en-1-ones by scandium(III) triflate-catalyzed fragmentation of 2-alkyl-3-iodo-1-oxocyclohexan-2,4-carbolactones

Co-reporter:Jun-ichi Matsuo, Mizuki Kawano, Kosuke Takeuchi, Hiroyuki Tanaka, Hiroyuki Ishibashi

Tetrahedron Letters 2009 50(17) pp: 1917-1919

Publication Date(Web):

DOI:10.1016/j.tetlet.2009.02.016

A practical synthesis of enantiopure N-carbobenzyloxy-N′-phthaloyl-cis-1,2-cyclohexanediamine by asymmetric reductive amination and the Curtius rearrangement

Co-reporter:Jun-ichi Matsuo, Masahiko Okano, Kosuke Takeuchi, Hiroyuki Tanaka, Hiroyuki Ishibashi

Tetrahedron: Asymmetry 2007 Volume 18(Issue 16) pp:1906-1910

Publication Date(Web):22 August 2007

DOI:10.1016/j.tetasy.2007.08.014

Enantiomerically pure N-carbobenzyloxy-N′-phthaloyl-cis-1,2-cyclohexanediamine was synthesized by the asymmetric reduction of a β-enamino ester formed from benzyl 2-oxocyclohexanecarboxylate and (R)-phenylethylamine, followed by hydrogenolysis, phthaloylation, and the Curtius rearrangement.(1S,2R)-2-Aminocyclohexanecarboxylic acidC7H13NO2Ee = >99%[α]D29=+20.2 (c 0.25, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)(1S,2R)-2-Phthalimidocyclohexanecarboxylic acidC15H15NO4Ee = >99%[α]D28=+98.3 (c 1.00, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)(1S,2R)-1-(N-Benzyloxycarbonylamino)-2-phthalimidocyclohexaneC22H22N2O4Ee = >99%[α]D29=+92.1 (c 0.10, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)(1S,2R)-1-(N-Benzyloxycarbonylamino)-2-acetamidecyclohexaneC16H22N2O3Ee = >99%[α]D29=+33.6 (c 0.10, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)

A mild and convenient synthesis of N-carbobenzyloxy ketimines

Co-reporter:Jun-ichi Matsuo, Yumi Tanaki, Aimi Kido and Hiroyuki Ishibashi

Chemical Communications 2006 (Issue 27) pp:2896-2898

Publication Date(Web):01 Jun 2006

DOI:10.1039/B605882E

N-Carbobenzyloxy (Cbz) ketimines were prepared conveniently from N-Cbz amines by oxidation with N-tert-butylbenzenesulfinimidoyl chloride.

Synthesis of various 6-substituted 1,4,5,6-tetrahydropyridazines by substitution of a 1,4,5,6-tetrahydro-6-tosylhydrazinopyridazines

Co-reporter:Shunya Morita, Jun-ichi Matsuo

Tetrahedron Letters (8 March 2017) Volume 58(Issue 10) pp:932-934

Publication Date(Web):8 March 2017

DOI:10.1016/j.tetlet.2017.01.069

Synthesis of multisubstituted phenols by formal [4 + 2] cycloaddition of nucleophilic alkynes with 3-ethoxycyclobutanones