Stereo- and Regiospecific Cu-Catalyzed Cross-Coupling Reaction of Vinyl Iodides and Thiols: A Very Mild and General Route for the Synthesis of Vinyl Sulfides

Kabir, M. Shahjahan; Linn, Michael L. Van; Monte, Aaron; Cook, James M.

doi:10.1021/ol801149n

Cited by 70 publications

(35 citation statements)

References 43 publications

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“…On the other hand, whereas 8 showed doublet peaks, 10 showed distorted doublet peaks (AB system): E ‐ 8 ( J = 12 Hz), Z ‐ 8 ( J = 5.3 Hz), E ‐ 10 ( J = 11.1 Hz). Such unusual small coupling constants of olefins were also observed in monohetereoatom‐substituted olefins, especially the oxygen‐substituted olefins (16,32,33).…”

Section: Resultsmentioning

confidence: 84%

Synthesis and Singlet Oxygen Reactivity of 1,2‐Diaryloxyethenes and Selected Sulfur and Nitrogen Analogs

Nkepang

Pogula

Bio

et al. 2012

Photochem & Photobiology

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1,2-Diaryloxyethene has recently been proposed as a linker in singlet oxygen-mediated drug release. Even though 1,2-diaryloxyethenes look very simple, their synthesis was not an easy task. Previous methods are limited to symmetric molecules, lengthy step and low yield. We report on a facile synthetic method not only for 1,2-diaryloxyethenes but also their sulfur and nitrogen analogs in yields ranging from 40 to 90% with more than 90% purity at the vinylation reaction.

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Section: Resultsmentioning

confidence: 84%

Synthesis and Singlet Oxygen Reactivity of 1,2‐Diaryloxyethenes and Selected Sulfur and Nitrogen Analogs

Nkepang

Pogula

Bio

et al. 2012

Photochem & Photobiology

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“…Because of the cost of palladium an alternative, viable and cheaper route was investigated in regard to the cross-coupling to provide ketone 10 . The recent report 55 on the copper-mediated preparation of vinyl sulfides encouraged use of the same catalytic system (CuI in combination with 1,2- cis -cyclohexanediol) for this cross-coupling reaction to obtain ketone 10 from vinyl iodide 22 . The treatment of 24 in combination with 50 mol% of CuI and 50 mol% of 1,2- cis -cyclohexanediol as a ligand and 2.0 equivalents of Cs 2 CO 3 as a base in DMF at 140 °C for 15 hours provided pentacyclic ketone 25 in 75% yield (Scheme 5).…”

Section: Resultsmentioning

confidence: 99%

Enantiospecific Total Synthesis of the Important Biogenetic Intermediates along the Ajmaline Pathway, (+)-Polyneuridine and (+)-Polyneuridine Aldehyde, as well as 16-Epivellosimine and Macusine A

et al. 2010

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The first stereospecific synthesis of polyneuridine aldehyde (6), 16-epi-vellosimine (7), (+)-polyneuridine (8), and (+)-macusine A (9) has been accomplished from commercially available D-(+)-tryptophan methyl ester. D-(+)-Tryptophan has served here both as the chiral auxiliary and the starting material for the synthesis of the common intermediate, (+)-vellosimine (13). This alkaloid was available in enantiospecific fashion in seven reaction vessels in 27% overall yield from D-(+)-trytophan methyl ester (14) via a combination of the asymmetric Pictet-Spengler reaction, Dieckmann cyclization, and a stereocontrolled intramolecular enolate-driven palladium-mediated cross-coupling reaction. A new process for this stereocontrolled intramolecular cross-coupling has been developed via a copper-mediated process. The initial results of this investigation indicated that an enolate driven palladium-mediated cross-coupling reaction can be accomplished by a copper-mediated process which is less expensive and much easier to work-up. An enantiospecific total synthesis of (+)-polyneuridine aldehyde (6), which has been proposed as an important biogenetic intermediate in the biosynthesis of quebrachidine (2), was then accomplished in an overall yield of 14.1% in 13 reaction vessels from D-(+)-tryptophan methyl ester (14). Aldehyde 13 was protected as the Na-Boc aldehyde 32 and then converted into the prochiral C (16)-quaternary diol 12 via the practical Tollens’ reaction and deprotection. The DDQ-mediated oxidative cyclization and TFA/Et3SiH reductive cleavage served as protection/deprotection steps to provide a versatile entry into the three alkaloids, polyneuridine aldehyde (6), polyneuridine (8) and macusine A (9) from the quarternary diol 12. The oxidation of the 16-hydroxymethyl group present in the axial position was achieved with the Corey-Kim reagent to provide the desired β-axial aldehydes, polyneuridine aldehyde (6) and 16-epi-vellosimine (7) with 100% diastereoselectivity.

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“…The suitable catalytic systems are [Cu(phen) (PPh 3 ) 2 ]NO 3 ( L13 ) ( Table 9.16 , entry 1) [78] , CuX/amino acid ( L1 and L2 ) (entries 2 and 3) [79,80] , and CuI/ cis -1,2 -cyclohexanediol ( L21 ) that was found recently to be a quite effi cient system (entry 4) [81] . Among them, CuI/ L21 led the reaction to occur at 30 -60 ° C, providing corresponding vinyl sulfi des in excellent yields, even from hindered and functional thiols.…”

Section: The Synthesis Of Alkenylsulfi Desmentioning

confidence: 99%

Copper‐Catalyzed Ligand Promoted Ullmann‐Type Coupling Reactions

Jiang

2010

Catalysis Without Precious Metals

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Stereo- and Regiospecific Cu-Catalyzed Cross-Coupling Reaction of Vinyl Iodides and Thiols: A Very Mild and General Route for the Synthesis of Vinyl Sulfides

Cited by 70 publications

References 43 publications

Synthesis and Singlet Oxygen Reactivity of 1,2‐Diaryloxyethenes and Selected Sulfur and Nitrogen Analogs

Synthesis and Singlet Oxygen Reactivity of 1,2‐Diaryloxyethenes and Selected Sulfur and Nitrogen Analogs

Enantiospecific Total Synthesis of the Important Biogenetic Intermediates along the Ajmaline Pathway, (+)-Polyneuridine and (+)-Polyneuridine Aldehyde, as well as 16-Epivellosimine and Macusine A

Copper‐Catalyzed Ligand Promoted Ullmann‐Type Coupling Reactions

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