Expedient Synthesis of 1,1-Diiodoalkenes

Bonnet, Béatrice; Gallic, Y. Le; Plé, G.; Duhamel, Lucette

doi:10.1055/s-1993-25999

Cited by 33 publications

(8 citation statements)

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“…27 The diiodide 22 was synthesized in 88% yield according to a literature procedure (eq 7). 28 Methyl (Z)-3-bromo-3-iodo-2-phenyl-propenoate (23) was prepared according to the reactions shown in Scheme 3. 25,29 The palladium-catalyzed annulation of a variety of internal alkynes using the above-mentioned vinylic iodides and triflates has been carried out as shown in eq 8.…”

Section: Table 1 (Continued)mentioning

confidence: 99%

Synthesis of Isocoumarins and α-Pyrones via Palladium-Catalyzed Annulation of Internal Alkynes

1999

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A number of 3,4-disubstituted isocoumarins and polysubstituted alpha-pyrones have been prepared in good yields by treating halogen- or triflate-containing aromatic and alpha,beta-unsaturated esters, respectively, with internal alkynes in the presence of a palladium catalyst. Synthetically, the methodology provides an especially simple and convenient, regioselective route to isocoumarins and alpha-pyrones containing aryl, silyl, ester, tert-alkyl, and other hindered groups. The reaction is believed to proceed through a seven-membered palladacyclic complex in which the regiochemistry of the reaction is controlled by steric factors. A number of 3,4-disubstituted isocoumarins and polysubstituted alpha-pyrones have been prepared in good yields by treating halogen- or triflate-containing aromatic and alpha,beta-unsaturated esters, respectively, with internal alkynes in the presence of a palladium catalyst. Synthetically, the methodology provides an especially simple and convenient regioselective route to isocoumarins and alpha-pyrones containing aryl, silyl, ester, tert-alkyl, and other hindered groups. The reaction is believed to proceed through a seven-membered palladacyclic complex in which the regiochemistry of the reaction is controlled by steric factors.

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Section: Table 1 (Continued)mentioning

confidence: 99%

Synthesis of Isocoumarins and α-Pyrones via Palladium-Catalyzed Annulation of Internal Alkynes

1999

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“…Corey and Fuchs reported in 1972 the use of dibromoalkene compounds as intermediates in the transformation of aldehydes to terminal alkynes . Although a wide series of 1,1-dibromo-1-alkenes or 1,1-diiodo-1-alkenes are easily prepared, , certain functionalized dibromides and diiodides cannot be synthesized in an efficient manner while other types of 1,1-dihalovinyl compounds such as mixed ( Z )- or ( E )-1-iodo-1-bromo alkenes are not accessible at all. The most useful procedures for the synthesis of compounds 3 and 4 are all conceptually similar because they use Wittig or related approaches.…”

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confidence: 99%

Hydrozirconation of Stannylacetylenes: A Novel and Highly Efficient Synthesis of 1,1-Diiodo-, 1,1-Dibromo-, and Mixed (Z)- or (E)-1-Iodo-1-bromo-1-alkenes Using 1,1-Hetero-Bimetallic Reagents

Dabdoub

Baroni

2001

J. Am. Chem. Soc.

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“…1,2 Etnangien together with the more readily available methyl ester 2, 3 present highly potent antibiotics, with average IC 50 values in the submicromolar range, both in vitro and in vivo. [1][2][3] They are effective against a broad panel of Gram-positive bacteria, especially those belonging to the actinomycetes.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Total Synthesis of Etnangien and Etnangien Methyl Ester

Arikan

et al. 2010

J. Org. Chem.

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ABSTRACT. A highly stereoselective joint total synthesis of the potent polyketide macrolide antibiotics etnangien and etnangien methyl ester was accomplished by a convergent strategy and proceeds in 23 steps (longest linear sequence). Notable synthetic features include a sequence of highly stereoselective substrate-controlled aldol reactions to set the characteristic assembly of methyl-and hydroxyl-bearing stereogenic centers of the propionate portions, an efficient diastereoselective Heck macrocyclization of a deliberately conformationally-biased precursor, and a late-stage introduction of the labile side chain by means of a high-yielding Stille coupling of protective-group free precursors.Along the way, an improved, reliable protocol for a Z-selective Stork-Zhao-Wittig olefination of aldehydes was developed and an effective protocol for a 1,3-syn reduction of sterically particularly hindered β-hydroxy ketones was devised. Within the synthetic campaign, a more detailed understanding of the intrinsic isomerisation pathways of these labile natural products was elaborated. The expedient and flexible strategy of the etnangiens should be amenable to designed analogues of these RNApolymerase inhibitors, thus enabling further exploration of the promising biological potential of these macrolide antibiotics.

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Expedient Synthesis of 1,1-Diiodoalkenes

Cited by 33 publications

References 0 publications

Synthesis of Isocoumarins and α-Pyrones via Palladium-Catalyzed Annulation of Internal Alkynes

Synthesis of Isocoumarins and α-Pyrones via Palladium-Catalyzed Annulation of Internal Alkynes

Hydrozirconation of Stannylacetylenes: A Novel and Highly Efficient Synthesis of 1,1-Diiodo-, 1,1-Dibromo-, and Mixed (Z)- or (E)-1-Iodo-1-bromo-1-alkenes Using 1,1-Hetero-Bimetallic Reagents

Stereoselective Total Synthesis of Etnangien and Etnangien Methyl Ester

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