Synthesis of (R)-(+)-Tanikolide through Stereospecific C-H Insertion Reaction of Dichlorocarbene with Optically Active Secondary Alcohol Derivatives

スポンサーリンク

概要

• 論文の詳細を見る

• Stereospecific α C-H insertion reaction of protected chiral 1,2-glycols, (S)-1,2-isopropylidenedioxytridecane (3) and ethyl (S)-4,5-isopropylidenedioxy-pentanoate (4), prepared from (R)-glyceraldehyde acetonide (2), with dichlorocarbene generated from CHCl_3/50% NaOH/cetyltrimethylammonium chloride (as ptc.) took place with complete retention of configuration to provide (S)-4-dichloromethyl-2,2-dimethyl-4-undecyl-1,3-dioxolane (5) and ethyl (S)-3-(4-dichloromethyl-2,2-dimethyl-1,3-dioxolan-4-yl)-propanoate (8), respectively. The ester (8) was transformed to 5 by elongation of the side chain. The glycol derivative (5) was converted into O-TBDPS-protected (S)-2-hydroxymethyl-2-undecyloxirane (16). Reaction of 16 with a cuprate reagent containing homoallylic carbon chain followed by oxidative manipulation of the terminal olefin afforded (R)-(+)-tanikolide (1).

• 公益社団法人日本薬学会の論文
• 2004-07-01

著者

• 正木 幸雄

  Gifu Pharmaceutical University

• MASAKI Yukio

  Gifu Pharmaceutical University

• ARASAKI Hideki

  Gifu Pharmaceutical University

• IWATA Masashi

  Gifu Pharmaceutical University

• MAKIDA Miyuki

  Gifu Pharmaceutical University

• 正木 幸雄

  岐阜薬科大学

• Iwata M

  Gifu Pharmaceutical University

関連論文

• メソポーラスシリカを活用する有機合成反応の開発に関する研究
• 不斉二級アルコール誘導体とジクロロカルベンの立体特異的C-H挿入反応を経る不斉四級炭素の構築
• 16 不斉ニトロオレフィン化反応を鍵反応とする光学活性フィゾスチグミンの合成(口頭発表の部)
• A Stable Crystalline (Alkylperoxy)iodinane : 1-(tert-Butylperoxy)-1,2-benziodoxol-3(1H)-one.
• Tetracyanoethylene-Hydrogen Peroxide, a Mild Epoxidation System of Olefins
• CATALYTIC ACTIVITIES OF DICYANOKETENE ACETALS IN ALCOHOLYSIS OF EPOXIDES
• Oxidative Photo-Decarboxylation in the Presence of Mesoporous Silicas
• Oxidative Transformation of Arylmethyl Bromides and Alcohols with a Combination of Mesoporous Silica FSM-16 and Alkali Iodides under Photoirradiation.
• Photooxidation of Arylmethyl Bromides with Mesoporous Silica FSM-16.
• New Synthetic Method of Imides through Oxidative Photodecarboxylation Reaction of N-Protected α-Amino Acids with FSM-16.
• Oxidative Photodecarboxylation of α-Hydroxycarboxylic Acids and Phenylacetic Acid Derivatives with FSM-16.
• New Synthetic Method of Imides through Oxidative Photodecarboxylation Reaction of N-Protected α-Amino Acids with FSM-16
• Synthesis of (R)-(+)-Tanikolide through Stereospecific C-H Insertion Reaction of Dichlorocarbene with Optically Active Secondary Alcohol Derivatives
• Stereospecific Construction of Chiral Quaternary Carbon Compounds from Chiral Secondary Alcohol Derivatives
• 研究開発情報 メソポーラスシリカを利用する有機合成反応
• Polymer-Supported Dicyanoketene Acetal as a π-Acid Catalyst : Monothioacetalization and Carbon-Carbon Bond Formation of Acetals.
• Polymer-Supported Dicyanoketene Acetal as a π-Acid Catalyst : Monothioacetalization and Carbon-Carbon Bond Formation of Acetals
• Unprecedented Polymer-supported π-Acid : Synthesis and Its Application as a Promoter to the Monothioacetalization of Acetals.
• Mild Esterification and Transesterification of Carboxylic Acids Catalyzed by Tetracyanoethylene and Dicyanoketene Dimethyl Acetal
• Mild Esterification and Transesterification of Carboxylic Acids Catalyzed by Tetracyanoethylene and Dicyanoketene Dimetheyl Acetal
• SYNTHESIS OF (+)-7-ETHYL-5-METHYL-6,8-DIOXABICYCLO[3,2,1]OCT-3-ENE, An OPTICALLY ACTIVE FORM OF THE HOUSE MOUSE PHEROMONE
• Pyridazino〔4,5-e〕-1,2,4-triazineの誘導体の合成と除草作用
• Studies on Syntheses and Reactions of Methoxypyridazines. II. Methoxylation of 3,4,6-Trichloropyridazine(Organic,Chemical)
• メソポーラスシリカを利用する有機合成反応
• 26 酒石酸を不斉源とする(+)-アスペルリンの全合成(口頭発表の部)
• Facile Synthesis of (E)-Allylic Alcohols by Acid-Catalyzed Modification of the Mislow-Evans Rearrangement of Allylic Sulfoxides
• Regio-and Stereoselective Terminal Allylic Carboxymethylation of gem-Dimethyl Olefins. Synthesis of Biologically Important Linear Degraded Terpenoids
• Synthetic Studies on Isoprenoidquinones. I. A Facile Regioand Stereocontrolled Synthesis of Protected Hydroquinones with an Omega-Hydroxyprenyl or Omega-Hydroxygeranyl Side Chain
• 高分子π酸触媒の開発
• Synthetic Studies on Isoprenoidquinones. II. Syntheses of Ubiquinone-10,Phylloquinone, and Menaquinone-4 by a Chain-Extending Method Utilizing Terminally Functionalized Isoprenoidhydroquinones
• HIGHLY STEREOSELECTIVE SYNTHESIS AND STRUCTURAL CONFIRMATION OF A FUNGAL METABOLITE, LL-P880β
• Preparation of Nitroalkenes : Substitution Reaction via Addition-Elimination Using β-Nitrovinyl Sulfoxides.
• Hard Acid and Soft Nucleophile Systems. Part 12. : Regioselective Functionalization of 1,3-Dienes through the Lewis Acid Mediated Thienium Cation Diels-Alder Reaction.
• Facile Synthesis of Optically Active Tertiary Alcohol Building Blocks by Stereospecific C-H Insertion Reaction of Dichlorocarbene with Secondary Alcohol Derivatives.
• Asymmetric Synthesis of (+)-Dihydrokawain-5-ol.
• Facile Synthesis of Optically Active Tertiary Alcohol Building Blocks by Stereospecific C - H Insertion Reaction of Dichlorocarbene with Secondary Alcohol Derivatives
• A highly asymmetric, Lewis Acid-catalysed Diels-Alder reaction using optically active 2-(3-tolyl-p-sulfinyl)furyl α, β-unsaturated ketones as a dienophile.
• Stereoselective Reduction of Chiral 3-(p-Tolylsulfinyl)-2-thienyl Ketones. : A Facile Entry to Optically Active Thienylcarbinols.
• Highly Stereoselective Hetero Diels-Alder Reactions of Chiral 3-(p-Tolylsulfinyl)-2-furaldehyde with Danishefsky's Diene Promoted by a Lanthanoid Lewis Acid.
• Stereoselective Reduction of Chiral 3-(p-Tolylsulfinyl)-2-thienyl Ketones. A Facile Entry to Optically Active Thienylcarbinols
• Total Synthesis of (+)-Asperlin Starting with (S, S)-Tartaric Acid.
• Total Synthesis of (+)-Asperlin Starting with (S,S)-Tartaric Acid
• Catalytic Activity of Isoborneol-Derived Sulfides in Asymmetric Addition of Diethylzinc to Benzaldehyde
• Addition-Elimination Strategy for Asymmetric Induction : A Chiral Sulfoxide as a Leaving Group.
• Deprotection of a Silyl Group with Mesoporous Silica
• New Synthetic Method of Benzaldehydes and α, β-Unsaturated Aldehydes with I_2under Photoirradiation.
• New Synthetic Method of Benzaldehydes and α,β-Unsaturated Aldehydes with I_2 under Photoirradiation
• Selective Deprotection of Triethylsilyl Group in the Presence of t-Butyldimethylsilyl Group with MCM-41/MeOH Heterogeneous System.
• Selective Acceleration for Deprotection of Benzyl Ethers with Ti-HMS
• Short-Step Synthesis of Chiral C_2-Symmetric 2,3,4,5-Tetrasubstituted Pyrrolidines from D-Mannitol and Their Use as Chiral Ligands in the Reaction of Diethylzinc and Benzaldehyde.
• Studies on Indolizines and Azaindolizines. I. The 1,3-Dipolar Cycloaddition of Acetylenic Compounds to Pyridazinium Ylides
• Synthesis and Investigation of C_2-Symmetric Optically Active Pyrrolidinium Salts as Chiral Phase-Transfer Catalysts
• Diastereoselective Imino-Aldol Condensation of Chiral 3-(p-Tolylsulfinyl)-2-furaldimine and Ester Enolates
• β-Lactam Synthesis by Diastereoselective Condensation of Chiral 3-(p-Tolylsulfinyl)-2-Furaldimine and Ester Enolates.
• Recoverable Chiral Sulfoxide : Remote Asymmetric Induction in Lewis Acid-Promoted Diels-Alder Reaction of Chiral Sulfinyl-Substituted Pyrrolylα, β-Unsaturated Enones.
• Remote Asymmetric Induction in Lewis Acid Catalyzed Diels-Alder Reaction of α, β-Unsaturated Enones Having a Chiral Sulfinyl-substituted, 5-Membered Aromatic Heterocycle.
• Remote Asymmetric Induction in Lewis Acid-Catalyzed Diels-Alder Reaction of α, β-Unsaturated Enones Having a Chiral Sulfinyl-Substituted, 5-Membered Aromatic Heterocycle
• Highly Stereoselective Aldol Reaction of Chiral 3-(p-Tolylsulfinyl)furfural with Silyl Ketene Acetal Catalyzed by Lanthanide Triflate
• Recoverable Chiral Sulfoxide : Asymmetric Diels-Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl)pyrrolyl α, β-Unsaturated Ketones as a Dienophile
• Diastereoselective Addition of Allyltriphenylstannane to 3-Sulfinylfurfural Mediated by Titanium (IV) Tetrachloride and Tin(IV) Tetrachloride.
• Alcoholysis of Epoxides Catalyzed by Tetracyanoethylene and Dicyanoketene Acetals.
• Alocoholysis of Epoxides Catalyzed by Tetracyanoethylene and Dicyanoketene Acetals
• Alcoholysis of Epoxides Catalyzed by Tetracyanoethylene
• Substrate-Specific Rearrangement and Acetonidation of Epoxy-Ethers Catalyzed by Tetracyanoethylen
• Substrate-Specific Rearrangement and Acetonidation of Epoxy-Ethers Catalyzed by Tetracyanoethylene
• α-Versus β-Elimination of (Z)-(β-Halovinyl)iododinium Salts : Generation of(α-Alkylidene)carbenes and Their Facile Intramolecular 1,2-Migration
• Michael Type Addition of Halides to Alkynyl(phenyl)iodonium Tetrafluoroborates. : Stereoselective Synthesis of (Z)-β-Halovinyl(phenyl)-iodonium Halides.
• Synthesis of (Z)-1,2-Dihalo-1-alkenes by the Reaction of (Z)-(β-Halovinyl)phenyliodonium Salts with n-Bu4NX or KX/CuX. Competitions between Nucleophilic Vinylic Substitutions and Aromatic Substitutions
• Synthesis of (Z)-1,2-Dihalo-1-alkenes by the Reaction of (Z)-(β-Halovinyl)phenyliodonium Salts with n-Bu_4NX or KX/CuX. : Competitions between Nucleophilic Vinylic Substitutions and Aromatic Substitutions.
• Nucleohilic Vinylic Substitutions of (Z)-(β-(Phenylsulfonyl)alkenyl) iodonium Tetrafluoroborates with Sodium Benzenesulfinate : Stereoselective Synthesis of (Z)-1,2-Bis(Phenylsulfonyl)alkenes
• Synthesis and Structure of 1-Alkynyl-1,2-benziodoxol-3(1H)-ones.
• Stereoselective Synthesis of Highly Labile(Z)-β-Alkylvinyl(phenyl) iodonium Perchlorates.
• Nucleophilic Vinylic Substitutions of (Z)-(β-(Phenylsulfonyl)alkenyl)-iodonium Tetrafluoroborates with Tetrabutylammonium Halides : Retention of Configuration.
• Synthesis and Structure of 1-(Diacetoxyiodo)-2,4,6-tri-tert-butylbenzen and Its Analogues.
• Inversion of Configuration in Nucleophilic Vinylic Substitutions of (E)-β-Alkylvinyliodonium Tetrafluoroborates with Halides.
• Generation of Allenyliodinanes and Their Reductive Indonio-Claisen Rearrangement.
• Synthesis of Chiral Hypervalent Organoiodinanes, Iodo(III)binaphthyls, and Evidence for Pseudorotation of Iodine.
• Synthesis of Chiral Sulfinyl-Substituted 1-Indolyl Enones and Asymmetric Conjugate Addition by an Arylcopper Reagent
• A Total Synthesis of (-)-Physostigmine.
• Tetracyanoethylene-Hydrogen Peroxide, a Mild Epoxidation System of Olefins.
• Ethyl Cyanoformate/Hydrogen Peroxide and Related Combination Systems, Novel Epoxidizing Systems of Olefins.
• Enantiospecific Synthesis of Optically Active Natural (+)-Conhydrine from (S, S)-Tartaric Acid.
• P-Anisyloxymethyl Group, a Novel Oxidatively Removable Acetal Type OH-Protecting Group.
• PB102 SYNTHESES OF THE OPTICALLY ACTIVE FORMS OF THE MUS MUSCULUS PHEROMONE
• Recyclable Polymeric π-Acid Catalyst Effective on Mannich-Type Reaction in Water
• Synthesis of (3S, 4S)-Statine and a Related Compound, (3S, 4S)-AHPPA, from D-Glucosamine as a Chiral Pool.
• Synthesis of (3S,4S)-Statine and a Related Compound, (3S,4S)-AHPPA, from _D-Glucosamine as a Chiral Pool
• Enantiospecific Synthesis of (3S, 4S)-Statine and Its Analogue from D-Glucosamine as a Chiral Pool.
• Enantiospecific Synthesis of (3S, 4S)-Statine and Its Analogue from D-Glucosamine as a Chiral Pool
• Chiral Synthesis of Dihydroxyamino Acid Moieties of AI-77-B and Calyculins from D-Glucosamine.
• Synthesis of D-erythro-Sphingosine from D-Glucosamine.
• Synthesis of Optically Active, Unusual, and Biologically Important Hydroxy-amino Acids from D-Glucosamine.
• Chiral Syntheses of Dihydroxyamino Acid Moieties of AI-77-B and Calyculins from D-Glucosamine
• Synthesis of D-erythro-Sphingosine from D-Glucosamine
• Participation of a Chain Mechanism in Efficient Monomerization of Dimethylthymine Cyclobutane Dimer Photosensitized by a Flavin in the Presence of Perchloric Acid
• Emissive Triplex Formation in a Methylene-Bridged A-D-D' System. Intramolecular Long-Range Electron Transfer^1
• Recoverable Chiral Sulfoxide : Asymmetric Diels-Alder Reaction Usig Optically Active 1-(2-p-Tolylsulfinyl) pyrrolyl α, β-Unsaturated Ketones as a Dienophile
• C_2-SYMMETRIC N-(β-MERCAPTOETHYL)PYRROLIDINE AS A CHIRAL CATALYST LIGAND IN THE ADDITION REACTION OF ALDEHYDES AND DIETHYLZINC
• 1, 6-Asymmetric Induction during the Conjugate Addition of Arylcopper Reagents to a Chiral Sulfinyl-Substituted Pyrrolyl α, β-Unsaturated Amide

もっと見る 閉じる

スポンサーリンク