Direct Reduction of Alcohols:  Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride

Yasuda, Makoto; Onishi, Yasunobu; Ueba, Masako; Miyai, Takashi; Baba, Akio

doi:10.1021/jo0158534

Cited by 188 publications

(96 citation statements)

References 14 publications

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“…It is very surprise to note that the tertiary alcoholic group was reduced in the presence of AC-Ni system. Yasuda et al (2001) reported the catalytic reduction of tertiary alcoholic group into alkane. Based on the literature, it is proposed that the C=C and C-OH group was reduced in the presence of AC-Ni catalyst system.…”

Section: Catalytic Reduction Of A-terpineolmentioning

confidence: 99%

Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

Ranchani

Parthasarathy

Devi³

et al. 2017

Appl Nanosci

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A novel Ni complexed aminoclay (AC) catalyst was prepared by complexation method followed by reduction reaction. Various analytical techniques such as FTIR spectroscopy, UV-visible spectroscopy, DSC, TGA, SEM, HRTEM, EDX, XPS and WCA measurement are used to characterize the synthesized material. The AC-Ni catalyst system exhibited improved thermal stability and fiber-like morphology. The XPS results declared the formation of Ni nanoparticles. Thus, synthesized catalyst was tested towards the Schiff base formation reaction between various bio-medical polymers and aniline under air atmosphere at 85°C for 24 h. The catalytic activity of the catalyst was studied by varying the % weight loading of the AC-Ni system towards the Schiff base formation. The Schiff base formation was quantitatively calculated by the 1 H-NMR spectroscopy. While increasing the % weight loading of the AC-Ni catalyst, the % yield of Schiff base was also increased. The k app and Ti values were determined for the reduction of indole and a-terpineol in the presence of AC-Ni catalyst system. The experimental results were compared with the literature report.

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Section: Catalytic Reduction Of A-terpineolmentioning

confidence: 99%

Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

Ranchani

Parthasarathy

Devi³

et al. 2017

Appl Nanosci

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“…Reduction of various alcohols. 16 Additionally, the system was found to give high chemoselectivity for hydroxyl groups in the presence of other functional groups, such as esters, as exemplified by the selective deoxygenation of hydroxy-esters (Scheme 10). Scheme 10.…”

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confidence: 99%

“…Direct chemoselective reduction of alcohols by Ph 2 SiHCl/InCl 3 . 16 It was proposed that InCl 3 acts as a Lewis acid that loosely coordinates to oxygen to accelerate the deoxygenation of the resulting intermediate by promoting a hydride transfer from silane. 16 While the generation of HInCl 2 was not reported in these earlier studies, the in situ formation of HInCl 2 may also explain the observed reductions.…”

mentioning

confidence: 99%

“…16 It was proposed that InCl 3 acts as a Lewis acid that loosely coordinates to oxygen to accelerate the deoxygenation of the resulting intermediate by promoting a hydride transfer from silane. 16 While the generation of HInCl 2 was not reported in these earlier studies, the in situ formation of HInCl 2 may also explain the observed reductions. Later studies of InCl 3 with other silanes including triethylsilane (Et 3 SiH), have proposed the in situ generation of HInCl 2 and its use in reductive aldol reactions (Scheme 11).…”

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confidence: 99%

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Synthesis of dichloroindium hydride and exploration of its reactivity with organic functional groups. Tandem, selective and partial reductions of halo-nitriles

Saavedra¹,

Bayrasy²,

Resendez³

et al. 2012

Arkivoc

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Dedicated to Professor Keith Smith on the occasion of his 65th anniversary AbstractMethods for the in situ generation of dichloroindium hydride (HInCl 2 ) via the reduction of InCl 3 with various reducing agents, such as tributyltin hydride (tributylstannane; Bu 3 SnH), diisobutylaluminum hydride (DIBAL-H), triethylsilane (Et 3 SiH), lithium aminoborohydride (LAB), and sodium borohydride (NaBH 4 ), in various solvents are reviewed and compared. The use of the InCl 3 /NaBH 4 system in addition to forming HInCl 2 , also generated borane that was trapped as BH 3 -tetrahydrofuran (THF). Carefully controlling the activity of these reducing agents allows for the selective and/or partial reduction of multi-functionalized compounds containing nitriles and halogens.

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“…[1][2][3] One of simple and useful methods involves conversion of hydroxy groups to the corresponding alkyl sulfonates, such as tosylates or mesylates, followed by reduction with hydride. As a hydride reagent, LiAlH 4 4 or LiBEt 3 H 5,6 is frequently used for this aim.…”

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confidence: 99%

Polycyclic Aromatic Compounds-mediated Electrochemical Reduction of Alkyl Mesylates

et al. 2006

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Electrochemical reduction of alkyl mesylates was successfully carried out by using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of biphenyl and t-BuOH. The reaction could proceed efficiently under mild conditions to give the corresponding alkanes in moderate to good yields. This procedure could also be applicable to chemoselective reduction of mesylates having functional groups such as epoxide, olefin, acetal, hydroxy, or cyano groups.Reduction of alcohols to the corresponding alkanes is an important transformation in organic synthesis. 1-3 One of simple and useful methods involves conversion of hydroxy groups to the corresponding alkyl sulfonates, such as tosylates or mesylates, followed by reduction with hydride. As a hydride reagent, LiAlH 4 4 or LiBEt 3 H 5,6 is frequently used for this aim. Their high reactivity, however, sometimes causes serious troubles such as over-reduction of other functional groups in the substrates. Therefore, chemoselective and widely applicable reduction of alkyl sulfonates under mild conditions would be still desirable although several alternative methods for the reduction of alkyl tosylates or mesylates have been developed. [7][8][9][10][11][12][13] On the other hand, electrochemical process can reduce various organic compounds under neutral and mild conditions. 14 While electrochemical reduction of alkyl tosylates predominantly gave the corresponding alcohols, 15 a similar reduction of alkyl mesylates gave the corresponding alkanes. Thus, electrochemical reduction of alkyl mesylates could take place efficiently by using a divided cell equipped with a lead cathode and a platinum anode to give the corresponding alkanes in good yields. 12 It was also reported that mesylates of -hydroxy esters could be reduced to the corresponding esters by indirect electrochemical reduction using diphenyl diselenide in a divided cell. 13 Although both electrochemical reactions could proceed under neutral and mild conditions to give the products in good yields, use of unfavorable metal as an electrode and a complicated divided cell could not be satisfactory from the view points of environmentally friendly organic synthesis. We tried electrochemical reduction by using a simple and easy-handled undivided cell equipped with a platinum cathode and a magnesium anode, and found that electrochemical reduction of alkyl mesylates could proceed efficiently in the presence of polycyclic aromatic compound such as naphthalene and biphenyl as an electron-transfer mediator to give the corresponding alkanes in moderate to good yields. In this communication, we wish to report polycyclic aromatic compounds-mediated electrochemical reduction of alkyl mesylates using an undivided cell.A constant current electrolysis of a DMF solution of dodesyl mesylate 1a containing 0.1 M Bu 4 NBF 4 using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode gave a 35:65 mixture of dodecane 2a and 1-dodecanol. Therefore, we tried the electrolysis in the presence of polycycli...

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Direct Reduction of Alcohols: Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride

Cited by 188 publications

References 14 publications

Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

Synthesis of dichloroindium hydride and exploration of its reactivity with organic functional groups. Tandem, selective and partial reductions of halo-nitriles

Polycyclic Aromatic Compounds-mediated Electrochemical Reduction of Alkyl Mesylates

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