Susumi Hatakeyama

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Organization: Nagasaki University

Department: Graduate School of Biomedical Sciences

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Organic Chemistry

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Chemicals
References

Stereoselective Construction of Entire Diastereomeric Stereotetrads Based on an Asymmetric Morita–Baylis–Hillman Reaction

Co-reporter:Hikaru Yoshimura;Jun Ishihara

European Journal of Organic Chemistry 2017 Volume 2017(Issue 19) pp:2719-2729

Publication Date(Web):2017/05/18

DOI:10.1002/ejoc.201700337

A method for the enantio- and diastereoselective construction of all possible stereoisomers of a polypropionate stereotetrad having four contiguous stereogenic centers has been developed. The approach features an iterative sequence of cinchona-alkaloid-catalyzed Morita–Baylis–Hillman reaction and subsequent diastereoselective hydrogenation. By this method, benzaldehyde was successfully converted into eight diastereoisomeric 3,5-dihydroxy-2,4-dimethyl-5-phenylpentanoic acid ester derivatives with high enantiomeric purities (99 % ee) in 25–67 % overall yield (eight steps) in a reagent-controlled manner.

Unified synthesis of tirandamycins and streptolydigins

Co-reporter:Hikaru Yoshimura, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

Chemical Communications 2015 vol. 51(Issue 95) pp:17004-17007

Publication Date(Web):29 Sep 2015

DOI:10.1039/C5CC07749D

The asymmetric total syntheses of tirandamycins A–D and tirandalydigin as well as the synthesis of the left-hand fragment of streptolydiginone and streptolydigin from a common intermediate are described. The comprehensive approach features the highly enantio- and diastereoselective assembly of the anti,anti,syn-stereotetrad unit which relies on a cinchona alkaloid-catalyzed asymmetric Morita–Baylis–Hillman reaction.

Total Synthesis of (−)-N-Methylwelwitindolinone C Isothiocyanate Based on a Pd-Catalyzed Tandem Enolate Coupling Strategy

Co-reporter:Keita Komine, Yusuke Nomura, Jun Ishihara, and Susumi Hatakeyama

Organic Letters 2015 Volume 17(Issue 15) pp:3918-3921

Publication Date(Web):July 27, 2015

DOI:10.1021/acs.orglett.5b01952

The highly stereocontrolled total synthesis of (−)-N-methylwelwitindolinone C isothiocyanate is described, which features the expeditious construction of a bicyclo[4.3.1]decane ring system by a palladium-catalyzed tandem enolate allylation/arylation reaction.

Formal [4 + 1]-Cycloaddition of Homopropargyl Alcohols to Diazo Dicarbonyl Compounds Giving Substituted Tetrahydrofurans

Co-reporter:Fumiya Urabe, Shohei Miyamoto, Keisuke Takahashi, Jun Ishihara, and Susumi Hatakeyama

Organic Letters 2014 Volume 16(Issue 3) pp:1004-1007

Publication Date(Web):January 13, 2014

DOI:10.1021/ol403746r

A novel formal [4 + 1]-cycloaddition of readily available homopropargyl alcohols with diazo dicarbonyl compounds is described, which involves tandem O–H insertion/Conia-ene cyclization under cooperative Rh(II)/Zn(II) catalysis. This reaction provides easy access to various substituted tetrahydrofurans and exhibits complete E-selectivity in the case of nonterminal alkynes.

The Absolute Configuration for Inthomycin C: Revision of Previously Published Work with a Reinstatement of the (3R)-Configuration for (−)-Inthomycin C

Co-reporter:Karl J. Hale, Susumi Hatakeyama, Fumiya Urabe, Jun Ishihara, Soraya Manaviazar, Milosz Grabski, and Maciej Maczka

Organic Letters 2014 Volume 16(Issue 13) pp:3536-3539

Publication Date(Web):June 24, 2014

DOI:10.1021/ol501484t

Stereochemical evidence is presented to demonstrate that (−)-inthomycin C has (3R)- and not (3S)-stereochemistry. Careful reappraisal of the previously published work2−5 now indicates that the Hatakeyama, Hale, Ryu, and Taylor teams all have synthesized (−)-(3R)-inthomycin C. The newly measured [α]D of pure (−)-(3R)-inthomycin C (98% ee) is −7.9 (c 0.33, CHCl3) and not −41.5 (c 0.1, CHCl3) as was previously reported in 2012.

Total Synthesis of Oxazolomycins

Co-reporter:Jun Ishihara

The Chemical Record 2014 Volume 14( Issue 4) pp:663-677

Publication Date(Web):

DOI:10.1002/tcr.201402009

Abstract

The oxazolomycin family of antibiotics, isolated from several Streptomyces strains, are intriguing molecules for synthesis due to their characteristic oxazole polyene lactam–lactone structures and significant antiviral, antibacterial, and antitumor biological activities. In the last ten years, we have been addressing synthetic problems to accomplish the total syntheses of neooxazolomycin and oxazolomycin A as well as the related antibiotics, inthomycins A, B, and C, which have truncated structures corresponding to the left-hand fragments. This account describes an overview of our synthetic efforts toward these natural products focusing on the strategies and methodologies we devised.

Total Synthesis of (−)-Cinatrin C1 Based on an In(OTf)3-Catalyzed Conia-Ene Reaction

Co-reporter:Fumiya Urabe, Shunsuke Nagashima, Keisuke Takahashi, Jun Ishihara, and Susumi Hatakeyama

The Journal of Organic Chemistry 2013 Volume 78(Issue 8) pp:3847-3857

Publication Date(Web):April 2, 2013

DOI:10.1021/jo400263w

The stereocontrolled total synthesis of (−)-cinatrin C1, a phospholipase A2 inhibitor, has been accomplished. The key feature includes the stereoselective construction of the highly substituted tetrahydrofuran core by In(OTf)3-catalyzed Conia–ene reaction of the oxygen-tethered acetylenic malonic ester followed by dihydroxylation with concomitant lactonization.

-Isocupreine, an Enantiocomplementary Catalyst of -Isocupreidine

Co-reporter:Yoshito Nakamoto;Fumiya Urabe;Dr. Keisuke Takahashi;Dr. Jun Ishihara ;Dr. Susumi Hatakeyama

Chemistry - A European Journal 2013 Volume 19( Issue 38) pp:12653-12656

Publication Date(Web):

DOI:10.1002/chem.201302665

Organocatalytic asymmetric syntheses of inthomycins A, B and C

Co-reporter:Madoka Yoshino, Kohei Eto, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 40) pp:8164-8174

Publication Date(Web):30 Aug 2012

DOI:10.1039/C2OB26084K

The total syntheses of (+)-inthomycin A, (+)-inthomycin B and (−)-inthomycin C, the oxazole-triene antibiotics isolated from Streptomyces sp., have been accomplished via the highly enantio- and stereoselective construction of the C1–C7 (iododienyl)aldol units by taking advantage of a Cinchona alkaloid-catalyzed asymmetric β-lactone synthesis and their isomerisation-free Stille coupling with (E)-5-(3-(tributylstannyl)allyl)oxazole.

Stereocontrolled Total Synthesis of (−)-Englerin A

Co-reporter:Keisuke Takahashi, Keita Komine, Yuichi Yokoi, Jun Ishihara, and Susumi Hatakeyama

The Journal of Organic Chemistry 2012 Volume 77(Issue 17) pp:7364-7370

Publication Date(Web):August 7, 2012

DOI:10.1021/jo301145r

The total synthesis of (−)-englerin A, a potent and selective inhibitor of renal cancer cell lines, is described. The key feature includes the stereocontrolled construction of the cyclopentane structure by taking advantage of a base-promoted epoxynitrile cyclization.

Total Synthesis of Oxazolomycin A

Co-reporter:Kohei Eto, Madoka Yoshino, Keisuke Takahashi, Jun Ishihara, and Susumi Hatakeyama

Organic Letters 2011 Volume 13(Issue 19) pp:5398-5401

Publication Date(Web):September 2, 2011

DOI:10.1021/ol202306d

The first total synthesis of oxazolomycin A, a structurally novel oxazole polyene γ-lactam/β-lactone antibiotic, is described. Key features include the stereocontrolled construction of the right-hand heterocyclic core by taking advantage of an In(III)-catalyzed Conia-ene type cyclization and the asymmetric synthesis of the left-hand segment starting with a Cinchona alkaloid-catalyzed cyclocondensation of an aldehyde with an acid chloride.

Organocatalytic asymmetric synthesis of quinine and quinidine

Co-reporter:Shaheen M. Sarkar, Yuko Taira, Ayako Nakano, Keisuske Takahashi, Jun Ishihara, Susumi Hatakeyama

Tetrahedron Letters 2011 Volume 52(Issue 8) pp:923-927

Publication Date(Web):23 February 2011

DOI:10.1016/j.tetlet.2010.12.066

Quinine and quinidine were synthesized by a highly enantio- and stereoselective approach starting from a proline-catalyzed asymmetric cycloaldolization of benzyl bis(2-formylethyl)carbamate which gave a 70:30 mixture of (3R,4R)-N-Cbz-3-hydroxymethyl-4-hydroxypiperidine (96% ee) and its 4S-epimer (92% ee) in 94% yield after in situ NaBH4 reduction.

Enantio- and stereoselective route to the phoslactomycin family of antibiotics: formal synthesis of (+)-fostriecin and (+)-phoslactomycin B

Co-reporter:Shaheen M. Sarkar, Everlyne N. Wanzala, Setsuya Shibahara, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

Chemical Communications 2009 (Issue 39) pp:5907-5909

Publication Date(Web):10 Aug 2009

DOI:10.1039/B912267B

A general methodology applicable for the synthesis of the phoslactomycin family of antibiotics, potent and selective protein phosphatase inhibitors, has been developed starting from a β-isocupreidine-catalyzed asymmetric Baylis–Hillman reaction of 3-(4-methoxybenzyloxy)propanal with hexafluoroisopropyl acrylate, and thereby formal syntheses of (+)-fostriecin and (+)-phoslactomycin B have been accomplished.

Entry to Heterocycles Based on Indium-Catalyzed Conia-Ene Reactions: Asymmetric Synthesis of ()-SalinosporamideA

Co-reporter:Keisuske Takahashi;Michiko Midori;Kei Kawano;Jun Ishihara Dr. Dr.

Angewandte Chemie 2008 Volume 120( Issue 33) pp:6340-6342

Publication Date(Web):

DOI:10.1002/ange.200801967

Entry to Heterocycles Based on Indium-Catalyzed Conia-Ene Reactions: Asymmetric Synthesis of ()-SalinosporamideA

Co-reporter:Keisuske Takahashi;Michiko Midori;Kei Kawano;Jun Ishihara Dr. Dr.

Angewandte Chemie International Edition 2008 Volume 47( Issue 33) pp:6244-6246

Publication Date(Web):

DOI:10.1002/anie.200801967

Total Synthesis of Neooxazolomycin

Co-reporter:Evans Otieno Onyango;Joji Tsurumoto;Naoko Imai;Keisuke Takahashi;Jun Ishihara Dr. Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 35) pp:

Publication Date(Web):31 JUL 2007

DOI:10.1002/anie.200702229

Two sides to the story: Neooxazolomycin, a member of the oxazolomycin family of antibiotics, was synthesized in naturally occurring form by a convergent approach. This highly stereoselective strategy consists of a Tamao hydrosilylation, palladium-catalyzed enolate alkenylation, dihydroxylation accompanied by lactonization, and a Nozaki–Hiyama–Kishi reaction to construct the right-hand segment as well as an improved route to the left-hand segment.

Total Synthesis of Neooxazolomycin

Co-reporter:Evans Otieno Onyango;Joji Tsurumoto;Naoko Imai;Keisuke Takahashi;Jun Ishihara Dr. Dr.

Angewandte Chemie 2007 Volume 119(Issue 35) pp:

Publication Date(Web):31 JUL 2007

DOI:10.1002/ange.200702229

Beidseitig gearbeitet: Neooxazolomycin, das zu den Oxazolomycin-Antibiotika gehört, wurde mit einem konvergenten Ansatz in der natürlich vorkommenden Form synthetisiert. Die hoch stereoselektive Strategie umfasst eine Tamao-Hydrosilylierung, eine palladiumkatalysierte Enolatalkenylierung, eine Dihydroxylierung mit Lactonbildung und eine Nozaki-Hiyama-Kishi-Reaktion für das rechte Segment sowie einen verbesserten Weg zum linken Segment.

Total Synthesis of (−)-Kaitocephalin Based on a Rh-Catalyzed C–H Amination

Co-reporter:Keisuke Takahashi ; Daisuke Yamaguchi ; Jun Ishihara

Organic Letters () pp:

Publication Date(Web):March 5, 2012

DOI:10.1021/ol300431n

A total synthesis of (−)-kaitocephalin, an ionotropic glutamate receptor antagonist, is accomplished in highly stereocontrolled manner via Overman rearrangement, rhodium-catalyzed benzylic C–H amination, pyrrolidine formation involving nucleophilic opening of a cyclic sulfamate, and rhodium-catalyzed allylic C–H amination as key steps.

Unified synthesis of tirandamycins and streptolydigins

Co-reporter:Hikaru Yoshimura, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

Chemical Communications 2015 - vol. 51(Issue 95) pp:NaN17007-17007

Publication Date(Web):2015/09/29

DOI:10.1039/C5CC07749D

Organocatalytic asymmetric syntheses of inthomycins A, B and C

Co-reporter:Madoka Yoshino, Kohei Eto, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 40) pp:NaN8174-8174

Publication Date(Web):2012/08/30

DOI:10.1039/C2OB26084K

Enantio- and stereoselective route to the phoslactomycin family of antibiotics: formal synthesis of (+)-fostriecin and (+)-phoslactomycin B

Co-reporter:Shaheen M. Sarkar, Everlyne N. Wanzala, Setsuya Shibahara, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama