Browse
Submit Data
Databases
API
Help

Dataset Information

42 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Iridium Catalyzed Hydro-hydroxyalkylation of Butadiene: Carbonyl Crotylation.

ABSTRACT: Exposure of alcohols 1a-1i to butadiene in the presence of a cyclometallated iridium catalyzed derived from allyl acetate, 4-methoxy-3-nitrobenzoic acid and BIPHEP (2,2'-bis(diphenylphosphino)biphenyl) results in hydrogen transfer to generate aldehyde-allyliridium pairs, which engage in C-C coupling to form products of carbonyl crotylation. Under related conditions using 1,4-butanediol as hydrogen donor, butadiene reductively couples to aldehydes 2e-2g and 2i to furnish carbonyl crotylation products 3e-3g and 3i. Thus, butadiene mediated carbonyl crotylation occurs with equal facility from the alcohol or aldehyde oxidation level with complete levels of branched regioselectivity.

SUBMITTER: Zbieg JR

PROVIDER: S-EPMC3001632 | biostudies-literature | 2010 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Iridium Catalyzed Hydro-hydroxyalkylation of Butadiene: Carbonyl Crotylation.

Zbieg Jason R JR Fukuzumi Takeo T Krische Michael J MJ

Advanced synthesis & catalysis 20101001 14-15

Exposure of alcohols 1a-1i to butadiene in the presence of a cyclometallated iridium catalyzed derived from allyl acetate, 4-methoxy-3-nitrobenzoic acid and BIPHEP (2,2'-bis(diphenylphosphino)biphenyl) results in hydrogen transfer to generate aldehyde-allyliridium pairs, which engage in C-C coupling to form products of carbonyl crotylation. Under related conditions using 1,4-butanediol as hydrogen donor, butadiene reductively couples to aldehydes 2e-2g and 2i to furnish carbonyl crotylation prod ...[more]

PMID: 21165157

Similar Datasets

Allenamide hydro-hydroxyalkylation: 1,2-amino alcohols via ruthenium-catalyzed carbonyl anti-aminoallylation.

Project description:Exposure of alcohols to allenamides in the presence of RuHCl(CO)(PPh(3))(3) and dippf [dippf = bis(diisopropylphosphino)ferrocene] results in hydrogen transfer to generate aldehyde-allylruthenium pairs, which engage in C-C coupling to form products of carbonyl aminoallylation as single anti-diastereomers.

| S-EPMC2881554 | biostudies-literature

Chiral-anion-dependent inversion of diastereo- and enantioselectivity in carbonyl crotylation via ruthenium-catalyzed butadiene hydrohydroxyalkylation.

Project description:The ruthenium catalyst generated in situ from H(2)Ru(CO)(PPh(3))(3), (S)-SEGPHOS, and a TADDOL-derived phosphoric acid promotes butadiene hydrohydroxyalkylation to form enantiomerically enriched products. Notably, the observed diastereo- and enantioselectivity is the opposite of that observed using BINOL-derived phosphate counterions in combination with (S)-SEGPHOS, the same enantiomer of the chiral ligand. Match/mismatch effects between the chiral ligand and the chiral TADDOL-phosphate counterion are described. For the first time, single-crystal X-ray diffraction data for a ruthenium complex modified by a chiral phosphate counterion are reported.

| S-EPMC3531795 | biostudies-literature

Enantioselective carbonyl allylation, crotylation, and tert-prenylation of furan methanols and furfurals via iridium-catalyzed transfer hydrogenation.

Project description:5-Substituted-2-furan methanols 1a-c are subject to enantioselective carbonyl allylation, crotylation and tert-prenylation upon exposure to allyl acetate, alpha-methyl allyl acetate, or 1,1-dimethylallene in the presence of an ortho-cyclometalated iridium catalyst modified by (R)-Cl,MeO-BIPHEP, (R)-C3-TUNEPHOS, and (R)-C3-SEGPHOS, respectively. In the presence of 2-propanol, but under otherwise identical conditions, the corresponding substituted furfurals 2a-c are converted to identical products of allylation, crotylation, and tert-prenylation. Optically enriched products of carbonyl allylation, crotylation, and reverse prenylation 3b, 4b, and 5b were subjected to Achmatowicz rearrangement to furnish the corresponding gamma-hydroxy-beta-pyrones 6a-c, respectively, with negligible erosion of enantiomeric excess.

| S-EPMC2830394 | biostudies-literature

Direct generation of acyclic polypropionate stereopolyads via double diastereo- and enantioselective iridium-catalyzed crotylation of 1,3-diols: beyond stepwise carbonyl addition in polyketide construction.

Project description:Under the conditions of transfer hydrogenation employing the cyclometalated iridium catalyst (R)-I derived from [Ir(cod)Cl](2), allyl acetate, 4-cyano-3-nitrobenzoic acid, and the chiral phosphine ligand (R)-SEGPHOS, α-methylallyl acetate engages 1,3-propanediol (1a) and 2-methyl-1,3-propanediol (1b) in double carbonyl crotylation from the alcohol oxidation level to deliver the C(2)-symmetric and pseudo-C(2)-symmetric stereopolyads 2a and 3a, respectively, with exceptional control of anti-diastereoselectivity and enantioselectivity. Notably, the polypropionate stereopentad 3a is formed predominantly as 1 of 16 possible stereoisomers. Desymmetrization of 3a is readily achieved upon iodoetherification to form pyran 4. The direct generation of 3a enables a dramatically simplified approach to previously prepared polypropionate substructures, as demonstrated by the synthesis of C19-C27 of rifamycin S (eight steps, originally prepared in 26 steps) and C19-C25 of scytophycin C (eight steps, originally prepared in 15 steps). The present transfer hydrogenation protocol represents an alternative to chiral auxiliaries, chiral reagents, and premetalated nucleophiles in polyketide construction.

| S-EPMC3154980 | biostudies-literature

Enhanced anti-diastereo- and enantioselectivity in alcohol-mediated carbonyl crotylation using an isolable single component iridium catalyst.

Project description:The cyclometalated iridium complex (S)-I derived from [Ir(cod)Cl](2), 4-cyano-3-nitrobenzoic acid, allyl acetate, and (S)-SEGPHOS is conveniently isolated by precipitation or through conventional silica gel flash chromatography. This single-component precatalyst allows alcohol mediated carbonyl crotylations to be performed at significantly lower temperature, resulting in enhanced levels of anti-diastereo- and enantioselectivity. Most significantly, the chromatographically isolated precatalyst (S)-I enables carbonyl crotylations that are not possible under previously reported conditions involving in situ generation of (S)-I.

| S-EPMC3064714 | biostudies-literature

Enantioselective iridium-catalyzed carbonyl isoprenylation via alcohol-mediated hydrogen transfer.

Project description:Highly enantioselective iridium catalyzed carbonyl (2-vinyl)allylation or "isoprenylation" is achieved via hydrogen auto-transfer or 2-propanol-mediated reductive coupling from primary alcohol or aldehyde reactants, respectively. Using this method, asymmetric total syntheses of the terpenoid natural products (+)-ipsenol and (+)-ipsdienol were achieved.

| S-EPMC6339811 | biostudies-literature

Diastereo- and Enantioselective Iridium Catalyzed Carbonyl (?-Cyclopropyl)allylation via Transfer Hydrogenation.

Project description:The first examples of diastereo- and enantioselective carbonyl ?-(cyclopropyl)allylation are reported. Under the conditions of iridium catalyzed transfer hydrogenation using the chiral precatalyst (R)-Ir-I modified by SEGPHOS, carbonyl ?-(cyclopropyl)allylation may be achieved with equal facility from alcohol or aldehyde oxidation levels. This methodology provides a conduit to hitherto inaccessible inaccessible enantiomerically enriched cyclopropane-containing architectures.

| S-EPMC4627847 | biostudies-literature

Diastereo- and enantioselective ruthenium-catalyzed hydrohydroxyalkylation of 2-silyl-butadienes: carbonyl syn-crotylation from the alcohol oxidation level.

Project description:Exposure of alcohols 2a-2j to 2-silyl-butadienes in the presence of ruthenium complexes modified by (R)-SEGPHOS or (R)-DM-SEGPHOS results in redox-triggered generation of allylruthenium-aldehyde pairs, which combine to form products of carbonyl crotylation 4a-4j in the absence of stoichiometric byproducts and with high levels of syn-diastereo- and enantioselectivity. In the presence of isopropanol under otherwise identical conditions, aldehydes 3a-3j are converted to an equivalent set of adducts 4a-4j. Whereas reactions conducted using conventional heating require 48 h, microwave irradiation enables full conversion in only 4 h. Finally, as illustrated in the conversion of adduct 4a to compounds 6a and 6b, diastereoselective hydroboration-Suzuki cross-coupling with aryl and vinyl halides followed by Fleming-Tamao oxidation enables generation of anti,syn-stereotriads found in numerous polyketide natural products.

| S-EPMC3131435 | biostudies-literature

Enantioselective C-H crotylation of primary alcohols via hydrohydroxyalkylation of butadiene.

Project description:The direct, by-product-free conversion of basic feedstocks to products of medicinal and agricultural relevance is a broad goal of chemical research. Butadiene is a product of petroleum cracking and is produced on an enormous scale (about 12 × 10(6) metric tons annually). Here, with the use of a ruthenium catalyst modified by a chiral phosphate counterion, we report the direct redox-triggered carbon-carbon coupling of alcohols and butadiene to form products of carbonyl crotylation with high levels of anti-diastereoselectivity and enantioselectivity in the absence of stoichiometric by-products.

| S-EPMC3439217 | biostudies-other

Hydrosilation of Carbonyl-Containing Substrates Catalyzed by an Electrophilic ?-Silane Iridium(III) Complex.

Project description:Hydrosilation of a variety of ketones and aldehydes using the cationic iridium catalyst, (POCOP)Ir(H)(acetone)(+), 1, (POCOP = 2,6-bis(di-tert-butyl phosphinito)phenyl) is reported. With triethyl silane, all but exceptionally bulky ketones undergo quantitative reactions employing 0.5 mol% catalyst in 20-30 min at 25 °C. Hydrosilation of esters and amides results in over-reduction and cleavage of C-O and C-N bonds, respectively. The diastereoselectivity of hydrosilation of 4-tert-butyl cyclohexanone has been examined using numerous silanes and is highly temperature dependent. Using EtMe(2)SiH, analysis of the ratio of cis:trans hydrosilation products as a function of temperature yields values for ??H(‡) (?H(‡) (trans) - ?H(‡) (cis)) and ??S(‡) (?S(‡) (trans) - ?S(‡)(cis)) of -2.5 kcal/mol and -6.9 e.u., respectively. Mechanistic studies show that the ketone complex, (POCOP)Ir(H)(ketone)(+), is the catalyst resting state and is in equilibrium with low concentration of the silane complex, (POCOP)Ir(H)(HSiR(3))(+). The silane complex transfers R(3)Si(+) to ketone forming the oxocarbenium ion, R(3)SiOCR'(2) (+), which is reduced by the resulting neutral dihydride 3, (POCOP)Ir(H)(2), to yield product R(3)SiOCHR'(2) and (POCOP)IrH(+) which closes the catalytic cycle.

| S-EPMC3092162 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data