99438-31-0Relevant academic research and scientific papers
Synthetic method of chiral alcohol compound with 6 carbon skeleton structure
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Paragraph 0034-0037, (2020/03/16)
To the invention, 6 pinene is used as the chiral auxiliary, and the chiral auxiliary compound (-) - a - is finally quenched and hydrolyzed to form the chiral alcohol pure, final product, with the purity 3, value, not only can obtain the target product, with high chiral purity and content, but also can carry out commercialized production, HPLC. 98.1%; The chiral alcohol compound has an. ideal yield 97.4%,e.e.
Versatile Homoallylic Boronates by Chemo-, SN2′-, Diastereo- and Enantioselective Catalytic Sequence of Cu?H Addition to Vinyl-B(pin)/Allylic Substitution
Lee, Jaehee,Torker, Sebastian,Hoveyda, Amir H.
supporting information, p. 821 - 826 (2017/01/13)
A highly chemo-, diastereo- and enantioselective catalytic method that efficiently combines a silyl hydride, vinyl-B(pin) (pin=pinacolato) and (E)-1,2-disubstituted allylic phosphates is introduced. Reactions, best promoted by a Cu-based complex with a chiral sulfonate-containing N-heterocyclic carbene, are broadly applicable. Aryl-, heteroaryl-, alkenyl-, alkynyl- and alkyl-substituted allylic phosphates may thus be converted to the corresponding homoallylic boronates and then alcohols (after C?B bond oxidation) in 46–91 % yield and in up to >98 % SN2′:SN2 ratio, 96:4 diastereomeric ratio and 98:2 enantiomeric ratio. The reasons why an NHC?Cu catalyst is uniquely effective (vs. the corresponding phosphine systems) and the basis for different trends in stereoselectivity are provided with the aid of DFT calculations.
Enantioselective syntheses of the proposed structures of cytotoxic macrolides iriomoteolide-1a and -1b
Ghosh, Arun K.,Yuan, Hao
body text, p. 3120 - 3123 (2010/09/16)
(Figure Presented) Enantioselective total syntheses of the proposed structures of macrolide cytotoxic agents iriomoteolide-1a and -1b have been accomplished. The synthesis was carried out in a convergent and stereoselective manner. However, the present wo
Synthesis and structure-activity correlation of natural-product inspired cyclodepsipeptides stabilizing F-actin
Tannert, Rene,Milroy, Lech-Gustav,Ellinger, Bernhard,Hu, Tai-Shan,Arndt, Hans-Dieter,Waldmann, Herbert
supporting information; experimental part, p. 3063 - 3077 (2010/05/15)
The fundamental role played by actin In the regulation of eukaryotic cell maintenance and motility renders it a primary target for small-molecule intervention. in this arena, a class of potent cytotoxic cyclodepsipeptide natural products has emerged over the last quarter-century to stimulate the fields of biology and chemistry with their unique actin-stabilizing properties and complex peptide-polyketide hybrid structures. Despite considerable research effort, a structural basis for the activity of these secondary metabolites remains elusive, not least for the lack of high-resolution structural data and a reliable synthetic route to diverse compound libraries. in response to this, an efficient solid-phase approach has been developed and successfully applied to the total synthesis of Jasplakinolide and chondramide C and diverse analogues. The key macrocylization step was realized using ruthenium-catalyzed ring-closing metathesis (RCM) that in the course of a library synthesis produced discernible trends in metathesis reactivity and E/Z-selectivity, After optimization, the RCM step could be operated under mild conditions, a result that promises to facilitate the synthesis of more extensive analogue libraries for structure-function studies. The growth inhibitory effects of the synthesized compounds were quantified and structure-activity correlations established which appear to be in good alignment with relevant biological data from natural products. in this way a number of potent unnatural and simplified analogues have been found. Furthermore, potentially important stereochemical and structural components of a common pharmacophore have been identified and rationalized using molecular modeling. These data will guide in-depth mode-of-action studies, especially into the relationship between the cytotoxicity of these compounds and their actin-perturbing properties, and should inform the future design of simplified and functionalized actln stabilizers as well.
MACROCYCLIC COMPOUNDS USEFUL AS INHIBITORS OF KINASES AND HSP90
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Page/Page column 111; 206, (2010/11/30)
Disclosed are macrocyclic compounds of formulae I-V,which are analogs of the pochonin resorcylic acid lactones, and processes for the preparation of the compounds. The compounds disclosed are useful as inhibitors of kinases and Heat Shock Protein 90 (HSP 90). Also disclosed are pharmaceutical compositions comprising an effective kinase-inhibiting amount or an effective HSP90-inhibiting amount of the compounds and methods for the treatment of disorders that are mediated by kinases and HSP90.
Synthesis of the C1-C17 macrolactone of tedanolide
Hassfeld, Jorma,Eggert, Ulrike,Kalesse, Markus
, p. 1183 - 1199 (2007/10/03)
The vinylogous Mukaiyama aldol reaction is a useful method to build up complex polyketide structures. It is successfully employed in the synthesis of the C1-C17 macrolactone of tedanolide, a highly cytotoxic marine natural product. These studies present a practical approach toward the total synthesis of tedanolide; it is pursued using the appropriate C13-C23 segment that is introduced by a pivotal aldol reaction to join both hemispheres.
Asymmetric allyl- and crotylboration with the robust, versatile, and recyclable 10-TMS-9-borabicyclo[3.3.2]decanes
Burgos, Carlos H.,Canales, Eda,Matos, Karl,Soderquist, John A.
, p. 8044 - 8049 (2007/10/03)
The remarkable versatility and selectivity of the 10-(trimethylsilyl)-9- borabicyclo[3.3.2]decanes (10-TMS-9-BBDs) in the allyl- and crotylboration of representative aldehydes are reported. The new reagents are prepared through air-stable crystalline pseudoephedrine borinic ester complexes of the 10-TMS-9-BBDs (4), which are available in 63% overall yield from B-MeO-9-BBN through a simple two-step procedure. These complexes 4 are directly converted to the corresponding B-allyl-10-TMS-9-BBDs (1) with allylmagnesium bromide, which either can be isolated (98%) or used in situ for the allylations. The remarkable enantioselectivity (96 to ≥99% ee) of these reagents in the rapid (3 h), asymmetric allylboration process at -78 °C is only slightly diminished when it is conducted at 25 °C, a phenomenon attributable to its rigid bicyclic structure. In addition to providing the homoallylic alcohols 6 efficiently (68-80%), the procedure also permits the efficient recovery of 4 (68-84%) for the direct regeneration of 1. Alternatively, an oxidative workup procedure can be used for the preparation of 6. The reagent gives predictable stereochemistry and exhibits an extremely high level of reagent control in the allylboration of D-glyceraldehyde acetonide. A simple and efficient procedure has been developed for the preparation of all four geometric and enantiomeric isomers of the B-crotyl-10-TMS-9-BBDs (10) from optically pure enantiomers of B-MeO-10-TMS-9-BBD (3). These reagents 10 also add rapidly (3 h) and efficiently to representative aldehydes at -78 °C, providing ready access to all four of the possible stereoisomers of the β-methyl homoallylic alcohols 12-15 (69-92%) in high dr (≥98:2) and ee (94-99%).
CHIRAL SYNTHESIS VIA ORGANOBORANES. 25. B-(Z AND E)-CROTYLBIS(2-ISOCARANYL)BORANES AS VALUABLE REAGENTS FOR THE ASYMMETRIC CROTYLBORATION OF ALDEHYDES
Brown, Herbert C.,Randad, Ramnarayan S.
, p. 4457 - 4462 (2007/10/02)
The asymmetric crotylboration of representative aldehydes, RCHO (R = Me, Et-), with B-(Z and E)-crotylbis(2-isocaranyl)boranes (4 and 5) proceeds with remarkably high enantioselectivity (>94-98 percent ee) and diastereoselectivity (>99 percent de) at -78 deg C in ethyl ether.
