Manabu Node

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The first enantioselective synthesis of imino-deoxydigitoxose and protected imino-digitoxose by using l-threonine aldolase-catalyzed aldol condensation

Co-reporter:Toshihiro Nishiyama, Tetsuya Kajimoto, Swapnil S. Mohile, Noboru Hayama, Teppei Otsuda, Minoru Ozeki, Manabu Node

Tetrahedron: Asymmetry 2009 Volume 20(Issue 2) pp:230-234

Publication Date(Web):12 February 2009

DOI:10.1016/j.tetasy.2008.12.029

Synthesis of dl-standishinal and its related compounds for the studies on structure–activity relationship of inhibitory activity against aromatase

Co-reporter:Takahiro Katoh, Taichi Akagi, Chie Noguchi, Tetsuya Kajimoto, Manabu Node, Reiko Tanaka, Manabu Nishizawa (née Iwamoto), Hironori Ohtsu, Noriyuki Suzuki, Koichi Saito

Bioorganic & Medicinal Chemistry 2007 Volume 15(Issue 7) pp:2736-2748

Publication Date(Web):1 April 2007

DOI:10.1016/j.bmc.2007.01.031

dl-Standishinal (1), an aromatase inhibitor isolated from Thuja standishii, was synthesized in 15 steps from p-formylanisole via aldol reaction of 12-hydroxy-6,7-secoabieta-8,11,13-trien-6,7-dial (2). In the present study, we found that the aldol condensation of 2 proceeded in excellent yield with the protonic catalyst such as d-camphorsulfonic acid in CH2Cl2. Moreover, structure-activity relationship of 1 and its related compounds was studied and it was revealed that the isomers having cis-configuration on the A/B-ring generally exhibited more potent inhibitory activities against aromatase than those with trans-configuration.

Development of odorless organosulfur reagents and asymmetric reaction using odorless thiols

Co-reporter:Manabu Node;Tetsuya Kajimoto

Heteroatom Chemistry 2007 Volume 18(Issue 5) pp:572-583

Publication Date(Web):10 JUL 2007

DOI:10.1002/hc.20348

Odorless organosulfur reagents were developed by increasing their molecular weights to suppress volatility. 1-Dodecanethiol (4), dodecyl methyl sulfide (5), p-heptylphenylmethanethiol (6), p-dodecylbenzenethiol (7), p-heptylbenzenethiol (8), 2-dodecyl-1,3-propanedithiol (11), p-octyloxyphenyl-methanethiol (18b), and p-octyloxybenzenethiol (19) are typical examples of the odorless thiols and sulfides. 6-Morpholinohexyl thiol (15), methyl 6-morpholinohexyl sulfide (16), and methyl 6-morpholinohexyl sulfoxide (17) were also developed as separable reagents from reaction products by facile acid-base extraction. In addition, p-tetramethylsilylphenylmethanethiol (18) and p-tetramethylsilylbenzenethiol (14) were synthesized as the odorless synthetic substitutes of benzyl mercaptan and benzenethiol, respectively. In a similar way, silylated diphenyl disulfide (26) and diselenide (27) were prepared as odorless disulfide and diselenide. Moreover, 10-sulfanylisoborneol (1) was found to be an excellent chiral odorless substitute of hydrogen sulfide in Michael addition. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:572–583, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20348

An efficient route for the synthesis of methyl (−)-1,4a-dimethyl-5-oxodecahydronaphthalene-1-carboxylate by using baker’s yeast-catalyzed asymmetric reduction

Co-reporter:Takahiro Katoh, Shinsuke Mizumoto, Masato Fudesaka, Masatoshi Takeo, Tetsuya Kajimoto, Manabu Node

Tetrahedron: Asymmetry 2006 Volume 17(Issue 11) pp:1655-1662

Publication Date(Web):17 July 2006

DOI:10.1016/j.tetasy.2006.06.015

Methyl (−)-1,4a-dimethyl-5-oxodecahydronaphthalene-1-carboxylate 1, a key synthetic intermediate for the synthesis of terpenoids, was efficiently synthesized by using a baker’s yeast-catalyzed asymmetric reduction of a σ-symmetrical 1,3-cyclohexanedione derivative.(−)-Methyl (E)-5-[(2R,3S)-3-hydroxy-2-methyl-1-oxocyclohexyl]-2-pentenoateC13H20O4[α]D20=-19.2 (c 1.06, CHCl3)(−)-(2S,3S)-1-Acetoxy-1,1-ethylnedioxy-2-methyl-2-(3-acetoxypropyl)cyclohexaneC16H26O6[α]D25=+23.7 (c 1.48, CHCl3)(+)-Methyl (E)-5-[(2R,3S)-3-(4-bromobenzoyloxy)-2-methyl-1-oxocyclohexyl]-2-pentenoateC20H23BrO5[α]D20=+44.4 (c 1.15, CHCl3)(+)-Methyl (E)-5-[(2R,3S)-(3-methoxymethoxy-2-methyl-1-oxocyclohexyl)]-2-pentenoateC15H24O5[α]D23=+1.9 (c 1.00, CHCl3)(+)-Methyl (2R,4aR,5S,8aS)-8a-hydroxy-5-methoxymethyl-4a-methyldeca-hydronaphthalene-1-carboxylateC15H26O5[α]D25=+75.6 (c 0.97, CHCl3)(−)-Methyl (2R,4aR,5S,8aR)-8a-hydroxy-5-methoxymethyl-4a-methyldecahdronaphthalene-1-carboxylateC15H26O5[α]D23=-31.9 (c 0.35, CHCl3)(+)-Methyl (4aR,5S)-5-methoxymethyl-4a-methyl-2,3,4,4a,5,6,7,8-octahydronaphthalene-1-carboxylateC15H24O4[α]D25=+149 (c 0.98, CHCl3)(−)-Methyl (2R,4aR,5S)-5-methoxymethyl-4a-methyl-1,2,3,4,4a,5,6,7-octahydronaphthalene-1-carboxylateC15H24O4[α]D22=-88.7 (c 0.87, CHCl3)(+)-Methyl (4aR,5S)-5-hydroxy-4a-methyl-2,3,4,4a,5,6,7,8-octahydronaphthalene-1-carboxylateC13H20O3[α]D25=+162 (c 0.44, CHCl3)(+)-Methyl (2S,4aR,5S,8aR)-5-methoxymethyl-1,4a-dimethyldecahydronaphthalene-1-carboxylateC16H28O4[α]D25=+27.6 (c 2.02, CHCl3)(+)-Methyl (2S,4aR,5S,8aR)-5-hydroxyl-1,4a-dimethyldecahydronaphthalene-1-carboxylateC14H24O3[α]D25=+20.2 (c 2.27, CHCl3)Methyl (4aR)-4a-methyl-5-oxo-2,3,4,4a,5,6,7,8-octahydronaphthalene-1-carboxylateC13H18O3[α]D23=+177 (c 0.98, CHCl3)(−)-Methyl (2S,4aR,8aR)-1,4a-dimethyl-5-oxodecahydronaphthalene-1-carboxylateC14H22O3[α]D25=-35.0 (c 0.82, CHCl3)

A practical improvement of odorless Corey–Kim and Swern oxidations

Co-reporter:Kiyoharu Nishide, Pranab K. Patra, Manabu Matoba, Kandasamy Shanmugasundaram and Manabu Node

Green Chemistry 2004 vol. 6(Issue 3) pp:142-146

Publication Date(Web):03 Feb 2004

DOI:10.1039/B312849K

Methyl 6-morpholinohexyl sulfide (3a, MMS) and methyl 6-morpholinohexyl sulfoxide (7, MMSO) have been employed as efficient odorless substitutes for dimethyl sulfide (DMS) and dimethyl sulfoxide (DMSO) in Corey–Kim and Swern oxidations, respectively. The oxidation products and the byproduct 3a are easily separable by simple aqueous extraction. The Corey–Kim oxidation was studied in various solvents. The utility of the odorless 6-morpholinohexan-1-thiol (2a) in the dealkylation of phenyl ethers and methyl esters is also presented.

Total Synthesis of (−)-Galanthamine by Remote Asymmetric Induction

Co-reporter:Sumiaki Kodama;Yoshio Hamashima Dr.;Kiyoharu Nishide Dr. Dr.

Angewandte Chemie 2004 Volume 116(Issue 20) pp:

Publication Date(Web):5 MAY 2004

DOI:10.1002/ange.200353636

Die entscheidende intramolekulare Michael-Addition zur Bildung des 5,7,5-Ringgerüsts von (−)-Galanthamin (1) gelang durch asymmetrische Ferninduktion eines von D-Phenylalanin abgeleiteten chiralen Imidazolidinon-Auxiliars (siehe Schema). Diese Totalsynthese von 1 verläuft im Unterschied zu früheren Synthesen nicht über das stark allergene Enon Narwedin.

Asymmetric reduction of methoxy substituted β-tetralones using transfer hydrogenation

Co-reporter:Muneto Mogi, Kaoru Fuji, Manabu Node

Tetrahedron: Asymmetry 2004 Volume 15(Issue 23) pp:3715-3717

Publication Date(Web):29 November 2004

DOI:10.1016/j.tetasy.2004.10.017

Asymmetric reductions of methoxy substituted 2-tetralones were studied. The asymmetric transfer hydrogenation reaction developed by Noyori using chiral η6-arene–ruthenium complexes (arene = p-cymene or benzene) was found to efficiently reduce various methoxy substituted 2-tetralones with >80% ee. Their enantiomeric excesses were found to depend on the position of the methoxy group and the types of the arene complexes. The conditions were identified for the asymmetric reduction of 8-methoxy-2-tetralone to the corresponding 2-tetralol in 98% ee, which was notably higher in enantioselectivity than the other methoxy substituted 2-tetralones.(2R)-8-Methoxy-2-tetralolC11H14O2[α]D27=+48.6 (c 0.27, EtOH), 98% eeAbsolute configuration: 2RSource of chirality: asymmetric reduction(2R)-7-Methoxy-2-tetralolC11H14O2[α]D27=+45.0 (c 0.22, EtOH), 88% eeAbsolute configuration: 2RSource of chirality: asymmetric reduction(2R)-6-Methoxy-2-tetralolC11H14O2[α]D27=+60.8 (c 0.42, EtOH), 92% eeAbsolute configuration: 2RSource of chirality: asymmetric reduction(2R)-5-Methoxy-2-tetralolC11H14O2[α]D27=+57.1 (c 0.45, EtOH), 88% eeAbsolute configuration: 2RSource of chirality: asymmetric reduction

Diastereo- and enantioselective synthesis of anti-1,3-mercapto alcohols from α,β-unsaturated ketones via tandem Michael addition–MPV reduction

Co-reporter:Minoru Ozeki, Kiyoharu Nishide, Fumiteru Teraoka, Manabu Node

Tetrahedron: Asymmetry 2004 Volume 15(Issue 5) pp:895-907

Publication Date(Web):8 March 2004

DOI:10.1016/j.tetasy.2004.01.020

A new and effective asymmetric synthesis of anti-1,3-mercapto alcohols 3 from α,β-unsaturated ketones 1 utilizing tandem Michael addition–Meerwein–Ponndorf–Verley (MPV) reduction is described. Transformation of the MPV products anti-4 via the Wagner–Meerwein rearrangement was optimized under acidic or basic conditions to afford 1,3-mercapto alcohols anti-3, depending on the substituent R2 of 4.Graphic(1R,3S)-1-Mercapto-1-phenyl-3-pentanolC11H16OS[α]D23=+120.9 (c 0.88, CHCl3)99% ee(1R,3R)-3-Mercapto-1,3-diphenyl-1-propanolC15H16OS[α]D25=+105.7 (c 0.77, CHCl3)99% ee

Total Synthesis of (−)-Galanthamine by Remote Asymmetric Induction

Co-reporter:Sumiaki Kodama;Yoshio Hamashima Dr.;Kiyoharu Nishide Dr. Dr.

Angewandte Chemie International Edition 2004 Volume 43(Issue 20) pp:

Publication Date(Web):5 MAY 2004

DOI:10.1002/anie.200353636

A pivotal intramolecular Michael addition to form a fused 5,7,5 ring system and the skeleton of (−)-galanthamine (1) was completely controlled by a remote chiral imidazolidinone auxiliary derived from D-phenylalanine (see scheme). This total synthesis of the allylic alcohol 1 avoids the corresponding enone narwedine, a highly allergenic intermediate in previous syntheses of 1.

One-Step Stereocontrol of Three Contiguous Stereogenic Centers in Acyclic Systems: The Tuning Effect of an Additive in a Tandem Asymmetric Michael Addition and Meerwein–Ponndorf–Verley Reduction

Co-reporter:Kiyoharu Nishide Dr.;Minoru Ozeki;Hideaki Kunishige;Yukihiro Shigeta;Pranab K. Patra Dr.;Yuri Hagimoto Dr. Dr.

Angewandte Chemie 2003 Volume 115(Issue 37) pp:

Publication Date(Web):25 SEP 2003

DOI:10.1002/ange.200351915

Bei Additions-Reduktions-Dominoreaktionen entstehen mit hoher Diastereoselektivität drei benachbarte Stereozentren. Das chirale Thiol 1 reagiert in einer Michael-Addition mit acyclischen α,β-disubstitutierten α,β-ungesättigten Ketonen 2 (siehe Schema). Bei der Untersuchung von Additiven stellte sich heraus, dass die Verbindungen 3 geeignete Vorstufen für die 1,3-Hydroxythiole 4 sind. R¹=Aryl, R²=Alkyl, R³=Alkyl oder Phenyl.

One-Step Stereocontrol of Three Contiguous Stereogenic Centers in Acyclic Systems: The Tuning Effect of an Additive in a Tandem Asymmetric Michael Addition and Meerwein–Ponndorf–Verley Reduction

Co-reporter:Kiyoharu Nishide Dr.;Minoru Ozeki;Hideaki Kunishige;Yukihiro Shigeta;Pranab K. Patra Dr.;Yuri Hagimoto Dr. Dr.

Angewandte Chemie International Edition 2003 Volume 42(Issue 37) pp:

Publication Date(Web):25 SEP 2003

DOI:10.1002/anie.200351915

A domino addition–reduction sequence to construct three contiguous stereogenic centers with a high level of diastereoselectivity makes use of the chiral camphor-derived thiol 1 in a Michael addition to acyclic α,β-disubstituted α,β-unsaturated ketones 2 (see scheme). The effect of additives was investigated, and it was also shown that compounds 3 are suitable precursors to 1,3-hydroxythiols of type 4. R¹=aryl, R²=alkyl, R³=alkyl or phenyl.

Recent development of asymmetric syntheses based on the Meerwein-Ponndorf-Verley reduction

Co-reporter:Manabu Node;Kiyoharu Nishide

Chirality 2002 Volume 14(Issue 10) pp:759-767

Publication Date(Web):18 OCT 2002

DOI:10.1002/chir.10142

Stereoselective Meerwein-Ponndorf-Verley (MVP) reductions, including intermolecular MPV reductions, intramolecular MPV reductions (asymmetric 1,5- and 1,7-hydride shifts), catalytic MPV reduction, and reactions related to the MPV reduction are reviewed from the standpoint of asymmetric synthesis. Chirality 14:759–767, 2002. © 2002 Wiley-Liss, Inc.

A new divergent synthesis of (+)- and (−)-ferruginine utilizing PLE-catalyzed asymmetric dealkoxycarbonylation

Co-reporter:Takahiro Katoh, Kiyoshi Kakiya, Takashi Nakai, Soichi Nakamura, Kiyoharu Nishide, Manabu Node

Tetrahedron: Asymmetry 2002 Volume 13(Issue 21) pp:2351-2358

Publication Date(Web):31 October 2002

DOI:10.1016/S0957-4166(02)00657-2

A new divergent synthesis of (+)- and (−)-ferruginine 4, via the optically active 8-benzyl-3-oxo-8-azabicyclo[3.2.1]octane-2-carboxylates 6 is described. The β-keto ester intermediates 6 were prepared by a novel PLE-catalyzed asymmetric dealkoxycarbonylation of the symmetric tropinone-type diesters 5. The key problem in the synthesis is controlling the regioselectivity of the reaction at the 2- and 4-positions in the tropane framework of the β-keto ester 6 for introduction of the acetyl group.Graphic

A novel intramolecular through-space interaction between F and CN: a strategy for the conformational control of an acyclic system

Co-reporter:Kiyoharu Nishide, Yuri Hagimoto, Hiroaki Hasegawa, Motoo Shiro and Manabu Node

Chemical Communications 2001 (Issue 22) pp:2394-2395

Publication Date(Web):02 Nov 2001

DOI:10.1039/B107213G

X-Ray crystallographic analyses of fluorocyanides anti-1 and 2 revealed a novel intramolecular through-space interaction between F and CN in an acyclic system, which was applied to a stereoselective protonation of acyclic fluorocyanides 2 having flexible conformation.

An Efficient Synthesis of (±)-Narwedine and (±)-Galanthamine by an Improved Phenolic Oxidative Coupling

Co-reporter:Manabu Node Dr.;Sumiaki Kodama;Yoshio Hamashima Dr.;Takahiro Baba;Norimitsu Hamamichi Dr.;Kiyoharu Nishide Assoc. Dr.

Angewandte Chemie 2001 Volume 113(Issue 16) pp:

Publication Date(Web):15 AUG 2001

DOI:10.1002/1521-3757(20010817)113:16<3150::AID-ANGE3150>3.0.CO;2-U

Alte Probleme, neue Lösungen! Die biomimetische Phenolkupplung von Norbelladinderivaten des Typs 1 (Bn = Benzyl), die zu dem Alzheimer-Therapeutikum Galanthamin 2 führt, wurde deutlich verbessert durch die Verwendung des Reagens PIFA, einer hypervalenten Iodverbindung (PIFA=Phenyliod(III)bis(trifluoracetat)).