- A simple enantioselective synthesis of (R)- and (S)-1,7-dioxaspiro[5.5]undecane via intramolecular asymmetric oxyselenenylation: A new route to optically active spiroketals
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Both enantiomers of 1,7-dioxaspiro[5.5]undecane, the major pheromone components of the olive fruit fly (Bactrocea oleae), have been synthesized by using a new method based on the intramolecular asymmetric oxyselenenylation of 4-(3,4-dihydro-2H-pyran-6-yl)butan-1-ol.
- Uchiyama, Masahiko,Oka, Masako,Harai, Satohide,Ohta, Akihiro
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Read Online
- Compact chiral environment biphenanthrene skeleton chiral phosphoric acid and preparation method and application thereof
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The invention discloses a diphenanthrene skeleton chiral phosphoric acid with a tight chiral environment, a preparation method thereof, and an application of the diphenanthrene skeleton chiral phosphoric acid as a catalyst in asymmetric synthesis of a chiral spiro ketal derivative. The chiral catalyst shows good catalytic activity and enantioselectivity in a reaction for asymmetrically synthesizing spiro ketal, and has a good industrial application prospect. The invention belongs to the field of asymmetric synthetic chemistry.
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Paragraph 0063-0065
(2022/03/02)
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- A new short synthesis of (±)-olean through cross metathesis
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A new synthesis of (±)-1,7-dioxaspiro[5.5]undecane (olean), the olive fruit fly pheromone, utilizing the cross-metathesis reaction as the key-step, is reported.
- Kranidiotis, Nektarios S.,Grammatoglou, Constantinos E.,Gallos, John K.
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p. 1441 - 1444
(2018/08/29)
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- Type II Anion Relay Chemistry: Exploiting Bifunctional Weinreb Amide Linchpins for the One-Pot Synthesis of Differentiated 1,3-Diketones, Pyrans, and Spiroketals
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The design, synthesis, and validation of new highly effective bifunctional linchpins for type II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative-charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one-pot preparation of monoprotected 1,3-diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work-up conditions.
- Farrell, Mark,Melillo, Bruno,Smith, Amos B.
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supporting information
p. 232 - 235
(2016/01/25)
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- CHIRAL IMIDODIPHOSPHATES AND DERIVATIVES THEREOF
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The invention relates to chiral imidodiphosphates and derivatives thereof having the general formula I, The compounds are suitable as chiral Br?nsted acid catalysts, phase-transfer catalysts, chiral anions for organic salts, metal salts or metal complexes for catalysis.
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- Chiral imidodiphosphates and derivatives thereof
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The invention relates to chiral imidodiphosphates and derivatives thereof having the general formula I, The compounds are suitable as chiral Br?nsted acid catalysts, phase-transfer catalysts, chiral anions for organic salts, metal salts or metal complexes for catalysis.
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Paragraph 0079; 0080; 0081; 0084; 0085
(2013/07/25)
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- Synthesis of donor-σ-perylenebisimide-acceptor molecules having PEG swallowtails and sulfur anchors
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Donor-σ-Acceptor (D-σ-A) molecules, arrayed in a monolayer between electrodes, can serve as molecular rectifiers. Using perylene-3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor allows the attachment of the donor group to one imide nitrogen and a solubilizing swallowtail, normally a long (e.g., C19) alkane connected at midchain, on the other. Such an alkyl tail facilitates the formation of Langmuir-Blodgett (LB) monolayers. We have employed several modified swallowtails to make new D-σ-A molecules: poly(ethylene glycol) (PEG) swallowtails with 6 ether oxygens or with 4 ether oxygens to promote hydrophilicity in orienting LB monolayers, and alkyl swallowtails ending with sulfur anchors (thioacetate, thiol, or methyl disulfide) to stabilize attachment of the D-σ-A molecules to gold electrodes. The preparation and characterization of D-σ-A molecules containing combinations of these swallowtails with pyrene, ferrocene, and tetramethylphenylenediamine donor groups is described.
- Kota, Rajesh,Samudrala, Ramakrishna,Mattern, Daniell Lewis
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p. 9641 - 9651
(2013/01/15)
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- A highly efficient access to spiroketals, mono-unsaturated spiroketals, and furans: Hg(II)-catalyzed cyclization of alkyne diols and triols
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Hg(II) salts are identified as highly efficient catalysts for the versatile construction of spiroketals from alkyne diols in aqueous conditions. Monounsaturated spiroketals and furans were accessed with equal ease when propargylic triols (or propargylic d
- Ravindar, Kontham,Sridhar Reddy, Maddi,Deslongchamps, Pierre
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p. 3178 - 3181
(2011/08/06)
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- Highly efficient catalytic routes to spiroketal motifs
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The versatile and efficient synthesis of a variety of spiroketal motifs via the double intramolecular hydroalkoxylation of aliphatic and aromatic alkyne diols was achieved using simple and readily accessible Ir(I) and Rh(I) cyclooctadiene complexes as cat
- Selvaratnam, Selvasothi,Ho, Joanne H.H.,Huleatt, Paul B.,Messerle, Barbara A.,Chai, Christina L.L.
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scheme or table
p. 1125 - 1127
(2009/05/27)
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- A palladium mediated spiroketal synthesis
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A Stork-Negishi olefination-coupling sequence has been applied to the synthesis of spiroketals.
- Conway, Jeremy C.,Quayle, Peter,Regan, Andrew C.,Urch, Christopher J.
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- Metal-catalyzed regioselective oxy-functionalization of internal alkynes: An entry into ketones, acetals, and spiroketals
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(Chemical Equation Presented) Platinum(II) and an unusual cationic gold(I) complex were identified as mild catalysts for the room temperature cycloisomerization or tandem hydroalkoxylation/acetal formation of unactivated internal alkynols. Under the appro
- Liu, Bo,De Brabander, Jef K.
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p. 4907 - 4910
(2007/10/03)
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- Palladium mediated spiroketal synthesis: Application to pheromone synthesis
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Stereospecific Stille coupling reactions of 2-metallo-dihydropyrans with Z-vinyl iodo alcohols and subsequent cyclisation provides rapid access to 1,7-dioxaspiro[5.5]undecane family of spiroketals.
- Conway, Jeremy C.,Quayle, Peter,Regan, Andrew C.,Urch, Christopher J.
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p. 11910 - 11923
(2007/10/03)
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- Alkynyltrifluoroborates as versatile tools in organic synthesis: A new route to spiroketals
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(Chemical Equation Presented) A simple and efficient two-step approach to spiroketals is described. Key steps include the preparation of functionalized hydroxyl α-alkynones by ring-opening reactions of lactones with lithium alkynyltrifluoroborates followed by a palladium-catalyzed hydrogenation/ spirocyclization of the prespiroketal intermediate.
- Doubsky, Jan,Streinz, Ludvik,Saman, David,Zednik, Jiri,Koutek, Bohumir
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p. 4909 - 4911
(2007/10/03)
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- Anomeric oxygen to carbon rearrangements of alkynyl tributylstannane derivatives of furanyl (γ)- and pyranyl (δ)-lactols
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Tetrahydropyran and tetrahydrofuran containing natural products, drugs and agrochemicals often possess carbon-carbon bonds adjacent to the heteroatom. Consequently, new methods for the construction of anomeric carbon-carbon bonds are of considerable importance. We have devised a new strategy to access these systems that requires the treatment of O-glycoside alkynyl tributylstannane derivatives of furanyl and pyranyl lactols with Lewis acid to effect oxygen to carbon rearrangements. This leads to the formation of the corresponding carbon linked alkynol products that can be further manipulated to produce key structural motifs and building blocks for the assembly of complex molecules.
- Buffet, Marianne F.,Dixon, Darren J.,Ley, Steven V.,Reynolds, Dominic J.,Storer, R. Ian
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p. 1145 - 1154
(2007/10/03)
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- [18O]-oxygen incorporation reveals novel pathways in spiroacetal biosynthesis by Bactrocera cacuminata and B. cucumis
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The origins of the oxygen atoms in 1,7-dioxaspiro[5.5]undecane (1) and hydroxyspiroacetal (2) from Bactrocera cacuminata, and in 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (3) and hydroxyspiroacetal (4) from B. cucumis, have been investigated by incorporati
- Fletcher, Mary T.,Wood, Barry J.,Brereton, Ian M.,Stok, Jeanette E.,De Voss, James J.,Kitching, William
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p. 7666 - 7667
(2007/10/03)
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- Syntheses of both enantiomers of 1,7-dioxaspiro[5.5]undecane: Pheromone components of the olive fruit-fly Dacus oleae from a new chiral intermediate, the (S(s))-2-(p-tolylsulfinyl)prop-2-en-1-ol
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Both enantiomers of 1,7-dioxaspiro[5.5]undecane, the pheromone components of the olive fruit-fly Dacus oleae have been synthesized from a new chiral sulfoxide, (Ss)-2-(p-tolylsulfinyl)prop-2-en-1-ol via hetero Diels-Alder reaction, chromatographic separation of the diastereomers on a silica gel column and desulfurization over Raney nickel as key steps.
- Hayes, Patricia,Maignan, Christian
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p. 783 - 786
(2007/10/03)
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- Selective rhenium-catalyzed oxidation of secondary alcohols with methyl sulfoxide in the presence of ethylene glycol, a convenient one-pot synthesis of ketals
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Formula presented Secondary alcohols are oxidized preferentially by DMSO and the catalyst ReOCl3(PPh3)2 in the presence of ethylene glycol and refluxing toluene, producing the corresponding ketals. The reactions are rapid, and proceed in very good to excellent yields. The byproducts of the reaction, methyl sulfide and water, are easily removed. No epoxidation or other common side reactions were observed. This direct oxidative transformation of alcohols to the protected ketal derivatives should have broad synthetic applicability.
- Arterburn, Jeffrey B.,Perry, Marc C.
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p. 769 - 771
(2008/02/12)
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- Process for the manufacture of spiroketals
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A process for the production of ambergris-type labdane spiroketals of general formulae I and II STR1 where R represents oxygen or sulphur, useful in the perfumery industry, the said process being characterized by the intramolecular cyclisation of the epox
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- 10-AZA-9-deoxo-11-deoxy-erythromycin A and derivatives thereof
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Compounds of the formula: STR1 where R is hydrogen, C1 -C10 alkylcarbonyl, or C1 -C10 alkyl which can be substituted by amino or cyano, R1 and R2 are independently hydrogen, hydroxyl or ami
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- Hydroxy-functionalized Conjugated Nitroolefins as Immediate Precursors of Spiroketals. A New Synthesis of 1,7-Dioxaspiroundecane and (E)-2-Methyl-1,7-dioxaspirododecane
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The syntheses of 1,7-dioxaspiroundecane 6a, the major component of sex pheromones of the fruit fly (Dacus oleae), and (E)-2-methyl-1,7-dioxaspirododecane 6b, a component of the pheromone of Andrena haemorrhoa, have been achieved in two steps in
- Ballini, Roberto,Petrini, Marino
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p. 3159 - 3160
(2007/10/02)
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- Synthesis of spiroacetal pheromones via metalated hydrazones
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The synthesis of simple alkyl substituted spiroacetals by α,α'-alkylation of metalated acetone dimethylhydrazone with appropriate electrophiles and subsequent acid catalyzed cleavage and ring closure of the products is described.
- Enders,Dahmen,Dederichs,Gatzweiler,Weuster
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p. 1013 - 1019
(2007/10/02)
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- DIASTEREO- AND ENANTIOSELECTIVE SYNTHESIS OF α,α'-DISUBSTITUTED SPIROACETALS USING THE SAMP-/RAMP-HYDRAZONE METHOD
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α,α'-Disubstituted spiroacetals were synthesized with excellent enantiomeric excesses and in good overal yields from symmetrical ketones employing the SAMP-/RAMP-hydrazone-method for asymmetric α,α'-alkylation.
- Enders, Dieter,Gatzweiler, Winfried,Dederichs, Eleonore
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p. 4757 - 4792
(2007/10/02)
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- Tosmic in the preparation of spiroacetals: Synthesis of pheromone components of olive fruit fly
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The dialkylated tosylmethyl isocyanide derivatives obtained by alkylation of TosMIC with halohydrin derivatives, on hydrolysis lead to the formation of 1,7-dioxaspiroalkanes.
- Yadav,Gadgil
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p. 6217 - 6218
(2007/10/02)
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- Synthetic Studies on Spiroketal Natural Products. II. An Enantioselective Synthesis of (R)- and (S)-1,7-Dioxaspiroundecane
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Both enantiomers of 1,7-dioxaspiroundecane, a chiral compound with C2 symmetry, were stereoselectively synthesized from an (R)-sulfoxide compound 8.The reaction of menthyl (S)-p-toluenesulfinate with a Grignard reagent gave the chiral sulfoxide (8), which was derived to a dihydropyran (12) by a several-step sequence.The base-catalyzed intramolecular Michael reaction of 12 exclusively afforded a dioxaspiro product (13) as a single stereoisomer.An acidic treatment of 13 resulted in isomerisation of the spiro center to give 14.Desulfurization of 13 and 14 over Raney nickel in the presence of sodium hydroxide gave (R)- and (S)-1,7-dioxaspiroundecane (R-1 and S-1), respectively. Keywords---asymmetric synthesis; chiral sulfoxide; insect pheromone; C2-symmetry; spiroketal; intramolecular Michael addition; 1,7-dioxaspiroundecane
- Iwata, Chuzo,Fujita, Masahiro,Kuroki, Toshio,Hattori, Kohji,Uchida, Shuji,Imanishi,Takeshi
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p. 3257 - 3263
(2007/10/02)
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- A NEWS SYNTHESIS OF SPIROACETALS VIA ALKYLIDENATION OF ESTER CARBONYLS WITH METAL CARBANE COMPLEXES
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Metal carbene complexes prepared from alkoxy-substitued 1,1-dibromalkanes react with alkoxy-substitued esters to give enol ether intermediates which undergo acid-catalysed methanolysis and cyclisation to spiroacetals in good overall yield.
- Mortimore, Michael,Kocienski, Philip
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p. 3357 - 3360
(2007/10/02)
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- Isolation and Synthesis of 1,7-Dioxaspiroundecane and 1,7-Dioxaspiroundecan-3- and -4-ols from the Olive Fly (Dacus oleae)
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The major component of the sex pheromone of the olive fly has been shown to be 1,7-dioxaspiroundecane (16).Two hydroxyspiroacetals, 1,7-dioxaspiroundecan-3- and -4-ols (17a) and (18a), have also been isolated from the rectal glands of the female
- Baker, Raymond,Herbert, Richard H.
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p. 1123 - 1128
(2007/10/02)
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- ALKYLATION REACTIONS OF ANIONS DERIVED FROM 2-BENZENESULPHONYL TETRAHYDROPYRAN AND THEIR APPLICATION TO SPIROKETAL SYNTHESIS
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Reaction of 3,4-dihydro-2H-pyran or 2-methoxytetrahydropyran with benzenesulphinic acid gave 2-benzenesulphonyl tetrahydropyran (1).Deprotonation of (1) followed by alkylation with carbonyl compounds or halides gave cyclic enol ether addition products by
- Ley, Steven V.,Lygo, Barry,Sternfeld, Francine,Wonnacott, Anne
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p. 4333 - 4342
(2007/10/02)
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- SYNTHESIS OF THE OPTICALLY ACTIVE FORMS OF 4,10-DIHYDROXY-1,7-DIOXASPIROUNDECANE AND THEIR CONVERSION TO THE ENANTIOMERS OF 1,7-DIOXASPIROUNDECANE, THE OLIVE FLY PHEROMONE
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Both the enantiomers of 1,7-dioxaspiroundecane, the major component of the pheromone of the olive fly (Dacus oleae), were synthesized from (S)-malic acid.
- Mori, Kenji,Uematsu, Tamon,Yanagi, Kazunori,Minobe, Masao
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p. 2751 - 2758
(2007/10/02)
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- SYNTHESIS OF THE ENANTIOMERS OF 1,7-DIOXASPIROUNDECANE, 4-HYDROXY-1,7-DIOXASPIROUNDECANE AND 3-HYDROXY-1,7-DIOXASPIROUNDECANE, THE COMPONENTS OF THE OLIVE FRUIT FLY PHEROMONE
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All of the enantiomers of the title compounds, the components of the pheromone of the olive fruit fly (Dacus oleae Gmelin), were synthesized from (S)-malic acid.
- Mori, Kenji,Watanabe, Hidenori,Yanagi, Kazunori,Minobe, Masao
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p. 3663 - 3672
(2007/10/02)
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- INTRAMOLECULAR MICHAEL ADDITION REACTION TO CHIRAL VINYLIC SULFOXIDES. AN ENANTIOSELECTIVE SYNTHESIS OF (R)- AND (S)-1,7-DIOXASPIROUNDECANE
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(R)- and (S)-1,7-Dioxaspiroundecane , sex pheromone of an olive fly, was each stereoselectively synthesized using an intramolecular Michael addition of hydroxyl group to a chiral vinylic sulfoxide moiety as an asymmetric induction step.
- Iwata, Chuzo,Fujita, Masahiro,Hattori, Kohji,Uchida, Shuji
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p. 2221 - 2224
(2007/10/02)
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- WITTIG AND HORNER-WITTIG COUPLING REACTIONS OF 2-SUBSTITUTED CYCLIC ETHERS AND THEIR APPLICATION TO SPIROKETAL SYNTHESIS
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Wittig and Horner-Wittig coupling reactions of tetrahydropyran or tetrahydrofuran 2-triphenylphosphonium salts or 2-diphenylphosphine oxides with aldehydes and lactols affords good yields of the corresponding enol ethers.In selected examples these enol ether products may be further converted to spiroketals some of which are natural pheromones derived from Dacus oleae and Paravespula vulgaris.
- Ley, Steven V.,Lygo, Barry,Organ, Helen M.,Wonnacott, Anne
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p. 3825 - 3836
(2007/10/02)
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- PREPARATION AND REACTIONS OF 2-BENZENESULPHONYLTETRAHYDROPYRAN
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The anion derived from 2-benzenesulphonyltetrahydropyran (1) reacts with various electrophiles to give alkylated or acylated products some of which are useful precursors for spiroketal synthesis.
- Ley, Steven V.,Lygo, Barry,Wonnacott, Anne
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p. 535 - 538
(2007/10/02)
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- A SIMPLE ROUTE TO SPIROKETALS VIA ALKYLATION OF DIHYDROPYRAN
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3,4-Dihydro-2H-pyran was alkylated, via its 2-lithio derivative, with several O-protected β- or γ-iodo alcohols in excellent yields.Acidic treatment of the resultant 2-substituted dihydropyrans produced both the deprotection of the hydroxyl group and the
- Amouroux, Roger
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p. 1489 - 1492
(2007/10/02)
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- SYNTHESIS OF THE ENANTIOMERS OF 1,7-DIOXASPIROUNDECANE AND 4-HYDROXY 1,7-DIOXASPIROUNDECANE, THE COMPONENTS OF THE OLIVE FLY PHEROMONE
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The enantiomers of the olive fly pheromone (1 and 4) were synthesized from (S)-malic acid in amounts sufficient for the biological test.
- Mori, Kenji,Uematsu, Tamon,Watanabe, Hidenori,Yanagi, Kazunori,Minobe, Masao
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p. 3875 - 3878
(2007/10/02)
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- ENOL ETHERS : PREPARATION AND SYNTHETIC APPLICATIONS
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A versatile preparation of α-alkoxyphosphonium bromides leading to enol ethers by Wittig coupling was exploited for the convergent synthesis of pheromones from the Douglas-fir tussock moth and the olive fly Dacus oleae as well as an oxaspirolactone and C-
- Ousset, J. B.,Mioskowski, C.,Yang, Y.-L.,Falck, J. R.
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p. 5903 - 5906
(2007/10/02)
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- 1,7-Dioxaspiroundecanes. An excellent system for the study of stereoelectronic effects (anomeric and exo-anomeric effects) in acetals
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Several isomeric compounds derived from the spiro systems 5 to 9 (Scheme 4) were obtained from the acid cyclization of the appropriate dihydroxy ketone precursor.The configuration and the conformation of the products obtained was determined by 13 C nmr analysis and equilibration studies.The experimental results can be rationalized by taking into account the anomeric and the exo-anomeric effects and the usual steric interactions.
- Deslongchamps, Pierre,Rowan, Daryl D.,Pothier, Normand,Sauve, Tilles
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p. 1105 - 1121
(2007/10/02)
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- Identification and Synthesis of the Major Sex Pheromone of the Olive Fly (Dacus oleae)
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The major component of the sex pheromone of the olive fly has been shown to be 1,7-dioxaspiroundecane (1) and its structure has been confirmed by unambiguous synthesis; field studies have confirmed its biological activity.
- Baker, Raymond,Herbert, Richard,Howse, Philip E.,Jones, Owen T.,Francke, Wittko,Reith, Wolfgang
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