Synthesis of enantiomerically enriched homoallylic alcohols and of 1,2-dien-1-ols using chiral tin(IV) complexes containing diethyl tartrate as an auxiliary ligand

Boldrini, Gian Paolo; Lodi, L.; Tagliavini, Emilio; Tarasco, Carmine; Trombini, Claudio; Umani‐Ronchi, Achille

doi:10.1021/jo00233a027

Cited by 71 publications

(14 citation statements)

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“…Ethyl 4‐hydroxy‐2‐methylene‐4‐phenylbutanoate (9 c) :59 Compound 9 c was obtained from benzaldehyde (0.5 mmol) and polymer 1 c as a colorless oil (100 mg, 91 %) after purification by flash chromatography (petroleum ether/ethyl acetate 88:12, R f = 0.10); 1 H NMR: δ = 1.32 (t, J = 7.2 Hz, 3 H), 2.66 (dd, J = 14.1, 8.4 Hz, 1 H), 2.78 (dd, J = 14.1, 4.2 Hz, 1 H), 2.92 (d, J = 3.6 Hz, 1 H), 4.20 (q, J = 7.2 Hz, 2 H), 4.87 (ddd, J = 8.4, 4.2, 3.6 Hz, 1 H), 5.58 (d, J = 1.2 Hz, 1 H), 6.22 (d, J = 1.2 Hz, 1 H), 7.23–7.37 (m, 5 H) ppm; 13 C NMR: δ = 14.2, 42.6, 61.1, 73.2, 125.7 (2×C), 127.5, 128.2, 128.4 (2×C), 137.2, 144.0, 167.8 ppm; IR (KBr): $\tilde \nu $ = 3460, 3074, 3030, 2981, 2960, 2929, 2872, 1715, 1630, 1500, 1455, 1193, 756, 700 cm −1 ; MS (EI, 70 eV): m/z (relative intensity): 220 (2), 175 (5), 174 (18), 157 (7), 129 (15), 114 (88), 107 (100), 105 (18), 86 (73), 79 (71), 77 (46), 69 (21), 68 (48), 40 (20), 29 (14).…”

Section: Methodsmentioning

confidence: 99%

Preparation of Allyltin Reagents Grafted on Solid Support: Clean and Easily Recyclable Reagents for Allylation of Aldehydes

Chrétien

Zammattio

Gauthier

et al. 2006

Chemistry A European J

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The preparation of polymer-supported allyltin reagents was shown to be possible for both unfunctionalized and functionalized allyl units. These reagents were treated with aldehydes in the presence of cerium(III) or indium(III) salts to afford high yields of homoallylic alcohols, practically uncontaminated with organotin residues (less than 5 ppm). Some mechanism aspects are briefly discussed and the potential for regeneration and reuse of these supported reagents is pointed out.

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Section: Methodsmentioning

confidence: 99%

Preparation of Allyltin Reagents Grafted on Solid Support: Clean and Easily Recyclable Reagents for Allylation of Aldehydes

Chrétien

Zammattio

Gauthier

et al. 2006

Chemistry A European J

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Section: Nih Public Accessmentioning

confidence: 99%

“…Additionally, the transfer hydrogenative protocol enables asymmetric carbonyl prenylation from the alcohol or aldehyde oxidation level, as demonstrated by the formation of identical sets of optically enriched adducts. This process constitutes an alternative to the use of stoichiometric metallic reagents in enantioselective carbonyl reverse prenylation [8][9][10][11][12] and represents the first use of allenes in enantioselective C-C bond forming transfer hydrogenation.Initial studies focused on the coupling of 1,1-dimethylallene 1a to aldehyde 2a. After extensive study, which involved a nearly exhaustive assay of commercial chelating chiral phosphine ligands, optical results (4a, 94% yield, 89% ee, Table 1) were achieved upon exposure of a toluene solution of 1a and 2a to the cyclometallated iridium C,O-benzoate derived from allyl acetate, m-nitrobenzoic acid and (S)-SEGPHOS 13 (eqn.…”

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confidence: 99%

Enantioselective Carbonyl Reverse Prenylation from the Alcohol or Aldehyde Oxidation Level Employing 1,1-Dimethylallene as the Prenyl Donor

Han¹,

Kim²,

Han³

et al. 2010

J. Am. Chem. Soc.

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Enantioselective transfer hydrogenation of 1,1-dimethylallene 1a in the presence of aromatic, α,β-unsaturated or aliphatic aldehydes 2a-2i mediated by isopropanol and employing a cyclometallated iridium C,O-benzoate derived from allyl acetate, m-nitrobenzoic acid and (S)-SEGPHOS delivers products of reverse prenylation 4a-4i in good to excellent isolated yields (65-96%) and enantioselectivities (87-93% ee). In the absence of isopropanol, enantioselective carbonyl reverse prenylation is achieved directly from the alcohol oxidation level to furnish an equivalent set of adducts 4a-4i in good to excellent isolated yields (68-94%) and enantioselectivities (86-91% ee). Competition and isotopic labeling experiments suggest rapid alcohol-aldehyde redox equilibration in advance of carbonyl addition, and capture of the kinetically formed π-allyl complex at a rate faster than reversible β-hydride elimination-hydrometallation. This protocol represents an alternative to the use of allylboron reagents in enantioselective carbonyl reverse prenylation and represents the first use of allenes in enantioselective C-C bond forming transfer hydrogenation.In the course of studies aimed at the development of C-C bond forming hydrogenations, 1-6 highly enantioselective carbonyl allylation3d,e and crotylation 3f employing allyl acetate and α-methyl allyl acetate as allyl and crotyl donors, respectively, were achieved under the conditions of iridium catalyzed transfer hydrogenation. For such reductive couplings, isopropanol is exploited as the hydrogen donor. Remarkably, primary alcohols may serve dually as hydrogen donors and aldehyde precursors, enabling carbonyl allylation or crotylation directly from the alcohol oxidation level.mkrische@mail.utexas.edu . Supporting information available: Experimental procedures, HPLC data, and spectral data for new compounds. Single crystal X-ray diffraction data for (S)-Ir-Complex I. This material is available free of charge via the internet at http://pubs.acs.org. With catalytic asymmetric methods for polyacetate and polypropionate construction in hand, an asymmetric prenylation protocol was sought. However, attempted use of allylic acetates as prenyl donors (2-methyl-3-butenyl acetate or 3-methyl-2-butenyl acetate) was unsuccessful. A potential solution to this problem resides in the use of 1,1-dimethylallene 1a as prenyl donor. However, in earlier studies on the iridium catalyzed reductive coupling of 1,1-dimethylallene 1a to aldehydes mediated by gaseous hydrogen, it was found that highly activated aldehydes were required and, despite an extensive assay of chiral phosphine ligands, only low levels of optical enrichment were observed. 3a NIH Public AccessHere, exploiting an ortho-cyclometallated iridium C,O-benzoate catalyst recently developed in our laboratory, 3e we report an efficient protocol for enantioselective catalytic carbonyl reverse prenylation employing 1,1-dimethylallene 1a as the prenyl donor under transfer hydrogenation conditions. 7 Unlike the related process employing ele...

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“…There are variety of methods for the construction of hydroxyallenes that include prototropic rearrangement of propargylic alcohols [14,15,16], metal-catalyzed nucleophilic addition of propargylic derivatives to aldehydes [17,18,19,20,21,22,23,24], Cu(I)-catalyzed reaction of propargylic chlorides with Grignard reagents [25,26,27], metal-catalyzed reaction of propargylic oxiranes with organometallic compounds [28,29,30,31,32,33,34,35] and ketones [36,37], reduction of alcohols, ethers, oxiranes etc. with aluminium reagents [38,39,40], Pd(0)-catalyzed reaction of cyclic carbonates with acetylenic compounds [41,42], S N 2’ [43,44] and A N [45,46,47] reactions of metalled alkoxy-allenes with oxiranes and ketones [5], and other routes [48,49].…”

Section: Introductionmentioning

confidence: 99%

Bifunctionalized Allenes. Part XIII. A Convenient and Efficient Method for Regioselective Synthesis of Phosphorylated α-Hydroxyallenes with Protected and Unprotected Hydroxy Group

2014

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Abstract:The paper describes a convenient and efficient method for regioselective synthesis of phosphorylated α-hydroxyallenes using an atom economical [2,3]-sigmatropic rearrangement of intermediate propargyl phosphites or phosphinites. These can be readily prepared via reaction of protected alkynols with dimethyl chlorophosphite or chlorodiphenyl phosphine respectively in the presence of a base.

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Synthesis of enantiomerically enriched homoallylic alcohols and of 1,2-dien-1-ols using chiral tin(IV) complexes containing diethyl tartrate as an auxiliary ligand

Cited by 71 publications

References 0 publications

Preparation of Allyltin Reagents Grafted on Solid Support: Clean and Easily Recyclable Reagents for Allylation of Aldehydes

Preparation of Allyltin Reagents Grafted on Solid Support: Clean and Easily Recyclable Reagents for Allylation of Aldehydes

Enantioselective Carbonyl Reverse Prenylation from the Alcohol or Aldehyde Oxidation Level Employing 1,1-Dimethylallene as the Prenyl Donor

Bifunctionalized Allenes. Part XIII. A Convenient and Efficient Method for Regioselective Synthesis of Phosphorylated α-Hydroxyallenes with Protected and Unprotected Hydroxy Group

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