- A simple synthesis of (-)-(R)-ipsdienol and (-)-(S)-ipsenol
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A short and efficient synthesis of the unnatural enantiomer of (+)-(S)- ipsdienol 1 and (-)-(S)-ipsenol 2 is presented via an asymmetric allylboration. The synthesis was achieved by using a one-pot reduction- methylenation of an exo-methylene lactone intermediate. (C) 1999 Elsevier Science Ltd.
- Draillard, Karine,Lebreton, Jacques,Villieras, Jean
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- A Facile Synthesis of Optically Pure (-)-(S)-Ipsenol Using a Chiral Titanium Complex
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A stereocontrolled synthetic route to optically pure (-)-(S)-ipsenol (I), the pheromone of Pityokteines curvidens and various other bark-beetle species is described.Key step of the synthesis is an enantioselective aldol reaction using a chiral titanium-carbohydrate complex (Scheme 1).The carboxylate function of the optically pure β-hydroxy acid 5 thus obtained in mol quantities is then elaborated to the diene moiety by standard methodology (Scheme 2).
- Oertle, Konrad,Beyeler, Harry,Duthaler, Rudolf O.,Lottenbach, Willi,Riediker, Martin,Steiner, Eginhard
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- A synthesis of S-(-)-ipsenol from lactic acid
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A six step synthesis of S-(-)-ipsenol, a constituent of the sex pheromone of the bark beetle, from lactic acid employs an asymmetric aldol condensation and a novel molybdenum catalyzed elimination of an allyl ester as key steps.
- Trost,Rodriguez
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- Intramolecular coupling of vinyl ether and olefins or acetylenes with Ti(II) reagent. Regio- and stereo-selective vinyltitanation of carbon-carbon multiple bonds
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Treatment of m-alkenyl (or m-alkynyl) vinyl ethers (m = 3,4) with a Ti(II) reagent generated most likely bicyclic oxatitana-cycles, which eliminate the alkoxide tether to effect the selective vinyltitanation of the alkene or alkyne moiety to give m-vinyl-
- Nakajima, Ryota,Urabe, Hirokazu,Sato, Fumie
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- Enantioselective Isoprenylboration Reaction of Aldehydes Catalyzed by a Chiral Phosphoric Acid
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The BINOL-derived chiral phosphoric acid (R)-TRIP is utilized as an organocatalyst in the asymmetric isoprenylboration reaction of aldehydes, wherein hydrogen-bond interactions play a key role in the control of enantioselectivity. A wide arrays of enantioenriched dienyl homoallyl alcohols, including two natural products (?)-Ipsdienol and (?)-Ipsenol, have been successfully constituted. The synthetic application to chiral isoprenylated isobenzofuranone, vinyloxirane and cyclohexene derivatives has also been disclosed. (Figure presented.).
- Zhang, Yu-Long,He, Bo-Jun,Xie, Yi-Wen,Wang, Yu-Hao,Wang, Yi-Long,Shen, Yong-Cun,Huang, Yi-Yong
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supporting information
p. 3074 - 3079
(2019/05/15)
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- METHOD FOR PRODUCING MONOTERPENE AND MONOTERPINOID COMPOUNDS AND USE THEREOF
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In various embodiments, the present disclosure provides a method and enzyme for forming various compounds, such as monoterpenes and monoterpenoid compounds. In a specific example, the present disclosure provides a method for producing one or more of (?)-ipsdienol, (?)-ipsenol, ipsenone, and ipsdienone. The present disclosure also provides methods of using compounds formed from the disclosed method and enzyme.
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Page/Page column 2; 4; 5
(2012/05/07)
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- Catalytic asymmetric allylic transfer reactions for the Enantioselective synthesis of dienyl and enynyl alcohols
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Efficient catalytic asymmetric allylic transfer reactions of achiral aldehydes with 2-ethynyl- and 2-ethenyl-2-propenyl-stannane promoted by BINOL-TiIV complex with synergetic reagent are achieved for the synthesis of homoenynyl- and dienyl alcohols with high levels of enantioselectivity. The range of enantioselectivity is 84-99% ee with good chemical yields. The application of catalytic asymmetric dienylation in a single operation was exemplified by the enantioselective synthesis of naturally occurring (-)-Ipsdienol and (-)-Ipsenol.
- Yu, Chan-Mo,Jeon, Miyoo,Lee, Jae-Young,Jeon, Junha
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p. 1143 - 1148
(2007/10/03)
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- Proline-catalyzed asymmetric aldol reactions between ketones and alpha-unsubstituted aldehydes.
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[reaction: see text] With this communication we extend the methodology of proline-catalyzed direct asymmetric aldol reactions to include alpha-unsubstituted aldehydes as acceptors. This important aldehyde class gives the corresponding aldols in 22-77% yield and up to 95% ee when the reactions are performed in pure acetone or in ketone/chloroform mixtures. On the basis of these results we have developed a concise new synthesis of (S)-ipsenol.
- List,Pojarliev,Castello
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p. 573 - 575
(2007/10/03)
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- Enantioselective synthesis of ipsenol and ipsdienol using a (2-bromoallyl)borane derivative
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(S)-(-)-Ipsenol and (S)-(+)-ipsdienol, a major component of the sex pheromone of the bark beetle, and their enantiomers were prepared enantioselectively using tartrate esters of (2-bromoallyl)boronic acid in the key step.
- Yamamoto, Yasunori,Hara, Shoji,Suzuki, Akira
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p. 1029 - 1036
(2007/10/03)
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- Optically active allylic tin reagent as an enantio-divergent synthon of isoprenoids via remote and divergent asymmetric induction
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(S)-2-(1-Hydroxymethyl)allyltin (1a) can be prepared in high enantiomeric purity. When its methylated and acetylated derivatives are allowed to add to aldehydes with the help of i-PrOTiCl3 and SnCl4, syn- and anti-homoallylic alcohol
- Nishigaichi, Yutaka,Kuramoto, Hiroki,Takuwa, Akio
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p. 3353 - 3356
(2007/10/02)
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- Intermediates useful for the chiral isoprenylation of aldehydes
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An improved process for preparing either optically pure enantiomer of the bark beetle pheromones ipsenol and ipsdienol is provided. The process is also applicable to the condensation of aldehydes of widely varying properties to the corresponding chiral alcohol. This invention also concerns novel intermediates R'2 B(2'-isoprenyl) wherein R' is isopinocampheyl, 2-isocaranyl and 4-isocaranyl.
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- Lewis Acid Promoted Ring-Opening Allylation of Epichlorohydrin with Allylic Silanes and Stannanes To Afford 1-Chloro-5-alken-2-ols. A Short Synthesis of (S)-(-)-Ipsenol
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Epichlorohydrine (1) was allylated in good yields with representative allylic silanes (2, 5, 7, 9) and stannanes (12, 18) in the presence of appropriate Lewis acids.The reaction proceeds with ring opening at the unsubstituted site in 1 and with allylic inversion in the allylating agents to give 1-chloro-5-alken-2-ols cleanly.A short synthesis of (S)-(-)-ipsenol (29) from 1 and an (allenylmethyl)silane (26) demonstrates the utility of this method in organic synthesis.
- Imai, Toshiro,Nishida, Shinya
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p. 4849 - 4852
(2007/10/02)
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- Chiral synthesis VIA organoboranes. 26. An efficient synthesis of isoprenyl derivatives of borane - Valuable reagents for the isoprenylboration of aldehydes. A convenient route to both enantiomers of ipsenol and ipsdienol in high optical purity
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Preparation of B-isoprenyldialkylboranes is achieved by adopting the Brandsma modification of the Schlosser procedure, namely metallation of isoprene with potassium 2,2,5,5-tetramethylpiperidide followed by sequential treatment with 5-methoxydialkylborane and boron trifluoride-etherate. These reagents are used for the convenient isoprenylation of aldehydes. Reaction of isovaleraldehyde and β, β-dimethylacrolein with B2′isoprenyldiisopinocampheylborane provides both ipsenol and ipsdienol, respectively in 65% yields and 96% ee.
- Brown, Herbert C.,Randad, Ramnarayan S.
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p. 4463 - 4472
(2007/10/02)
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- B-2'-ISOPRENYLDIISOPINOCAMPHEYLBORANE: AN EFFICIENT REAGENT FOR THE CHIRAL ISOPRENYLATION OF ALDEHYDES. A CONVENIENT ROUTE TO BOTH ENANTIOMERS OF IPSENOL AND IPSDIENOL
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B-2'-Isoprenyldiisopinocampheylborane is prepared by metallation of isoprene with potassium 2,2,5,5-tetramethylpiperidide followed by sequential treatment with B-methoxydiisopinocampheylborane and boron trifluoride-etherate.Condensation of this reagent with aldehydes provides isoprenylated chiral alcohols.This methodology is utilized for an efficient one-pot synthesis of both enantiomers of the pheromones of the bark beetle Ips paraconfusus Lanier, ipsenol and ipsdienol in 96percent ee and 65percent isolated yields.
- Brown, Herbert C.,Randal, Ramnarayan S.
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p. 455 - 458
(2007/10/02)
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- Metal complexes containing optically active sugar ligands, a process for their preparation and their use as chiral reactants for synthesis of alcohols and amines
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Compounds of the forulae I and Ia STR1 in which R1 is a group which can be transferred to carbonyl or imine compounds, for example alkyl, allyl, vinyl or the radical of an enol or enamine, R2 is, for example, cyclopentadienyl, R3 is the radical of an optically active sugar or sugar derivative, Me is Ti, Zr or Hf, x is 0, 1 or 2 and y is 0, 1, 2 or 3, M≈ is Li≈, Na≈, K≈, MgY≈, ZnY≈, CdY≈, HgY, CuY≈ or quaternary ammonium, Y being halogen, are suitable for use as chiral reactants for compounds containing aldehyde, keto and/or N-substituted imine groups.
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- Chiral Allenylboronic Esters as a Practical Reagent for Enantioselective Carbon-Carbon Bond Formation. Facile Synthesis of (-)-Ipsenol
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A stereospecific synthetic route to (-)-ipsenol is described.The synthesis illustrates a new asymmetric synthetic reaction using chiral allenyl boronic esters.The scope of the synthesis as a general route to either (R)- or (S)-3-alkynol is further illustrated by several cases.
- Ikeda, Nobuo,Arai, Isao,Yamamoto, Hisashi
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p. 483 - 486
(2007/10/02)
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