A Mild and Convenient Method for the Reduction of Organic Halides by Using a SmI2-THF Solution in the Presence of Hexamethylphosphoric Triamide (HMPA)

Inanaga, Junji; Ishikawa, Mitsuhiro; Yamaguchi, Masaru

doi:10.1246/cl.1987.1485

Cited by 276 publications

(97 citation statements)

References 5 publications

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“…[24] CarbonϪ halogen bonds were effectively and quantitatively reduced to CϪH bonds by a mixture of SmI 2 -HMPA in THF (Scheme 11). Alkyl, vinyl and aryl halides were rapidly reduced, with approximately 5% HMPA as co-solvent in THF.…”

Section: Smi 2 -Hmpa-mediated Reductions the Effect Of Hmpa On Varioumentioning

confidence: 99%

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

2004

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Samarium(II) iodide is a one‐electron transfer reagent that has become highly appreciated as a mild and selective reducing agent in recent years. It has been found experimentally that various additives and co‐solvents largely control the reactivity of SmI2. This microreview provides an overview of the current knowledge of the reagent SmI2 as a reducing agent, in particular with additives that increase its reactivity. The use of various proton sources is covered, as well as the effect of co‐solvents. Furthermore, the very powerful reagent mixture SmI2/H2O/amine is also described. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Smi 2 -Hmpa-mediated Reductions the Effect Of Hmpa On Varioumentioning

confidence: 99%

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

2004

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“…In some cases, however, deoxygenation of the sulfinyl group with Zn-TiCl 4 did not proceed without hydrolysis of the ester group; therefore, deoxygenation was carried out by SmI 2 -HMPA. 75) …”

Section: Ethyl (3r/3s)-3-(n-p-methoxyphenylamino)-22-dimethyl-3-[(s mentioning

confidence: 99%

Diastereoselective Imino-Aldol Condensation of Chiral 3-(p-Tolylsulfinyl)-2-furaldimine and Ester Enolates.

Arai

Yoneda

Masuda

et al. 2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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The biological importance of b-lactams as antibiotics has stimulated the development of efficient procedures for the preparation of this class of compounds. Of the synthetic routes to b-lactams that have been reported, Lewis acid-promoted [1][2][3] and catalyzed [4][5][6][7][8][9][10][11] condensations of imines with silyl ketene acetals and imino-aldol condensations with ester enolates are powerful methods which involve the efficient construction of stereogenic centers of the b-lactam moiety.12-14) Chiral versions of these condensations have also been devised by the use of imines with a chiral auxiliary, [1][2][3][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] chiral ester enolate derivatives, [30][31][32][33][34][35][36] and chiral Lewis acids. [37][38][39][40][41] In the course of our studies on remote asymmetric induction using chiral sulfoxides, we previously reported the lanthanoid triflate-catalyzed Mukaiyama aldol reaction of sulfinyl aldehyde 1 with silyl ketene acetals.42) Highly remote stereocontrol of 1 in this reaction led us to examine an enantioselective route to b-lactams by diastereoselective condensation of an aldimine 2 derived from 1 with silyl ketene acetals as well as enolates. We would like to report the details of this condensation using the sulfinyl furaldimine 2. 43)Initial experiments were performed with a typical silyl ketene acetal 3a in the presence of a lanthanoid triflate, which is found to be effective for the aldol condensation of the aldehyde 1. 42) In fact, the reaction using Yb(OTf) 3 proceeded smoothly; diastereoisomeric b-amino esters 4a and 6a were produced in a ratio of 1 : 1 (Table 1, entry 1).44) The use of other lanthanoid triflates did not improve the diastereoselectivity. The relative stereochemistry of the two products 4a and 6a was not determined at this stage; however, the configuration at the C(3) position was later determined (vide infra). We then turned our attention to using an ester enolate

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“…This reaction is used in modern organic chemistry for the purpose of reduction of halides to hydrocarbons [14,15].…”

Section: Introductionmentioning

confidence: 99%

New and improved routes to alkoxyamine initiators for controlled radical polymerisation

Thiessen¹,

Wolff²

2005

Designed Monomers and Polymers

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Abstract-O-substituted hydroxylamines were synthesized in almost quantitative yields using ultrasound and Mn(OAc) 3 (in substance or regenerated in situ by an oxidizing agent) as electron-transfer agent. Two novel synthetic methods for the synthesis of alkoxyamines from organic halides and stable nitroxide radicals are introduced. One of them utilises cyancobalamine (vitamine B 12 ), the other SmI 2 as catalyst and magnesium metal as reductive agent. The yields are good for the first method and excellent for the second. The initiators were tested in controlled radical polymerisation of styrene, methylmethacrylate and 4-vinylpyridine.

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A Mild and Convenient Method for the Reduction of Organic Halides by Using a SmI2-THF Solution in the Presence of Hexamethylphosphoric Triamide (HMPA)

Abstract: A remarkable effect of HMPA was observed in the reduction of organic halides with a SmI2-THF solution. Various types of organic halides were reduced rapidly to the corresponding alkanes in almost quantitative yields under mild reaction conditions.

Cited by 276 publications

References 5 publications

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

Samarium(II) Iodide Mediated Reductions − Influence of Various Additives

Diastereoselective Imino-Aldol Condensation of Chiral 3-(p-Tolylsulfinyl)-2-furaldimine and Ester Enolates.

New and improved routes to alkoxyamine initiators for controlled radical polymerisation

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