Homomolecular esterification of aldehydes catalyzed by hydridotetrakis(triphenylphosphine)rhodium(I)

Massoui, Mohamed; Beaupère, D.; Nadjo, Louis; Uzan, R.

doi:10.1016/0022-328x(83)87185-x

Cited by 21 publications

(8 citation statements)

References 18 publications

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“…In earlier work, 9 we have shown that RhH(PPh 3 ) 4 induced an intramolecular esterification of a dialdehyde derivative. In the case of itols, it was difficult to assume that a dialdehyde might be the intermediate, as this hypothesis required the simultaneous oxidation of the two primary alcohol functions.…”

Section: Letters Synlettmentioning

confidence: 98%

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

Isaac¹,

Aizel²,

Stasik³

et al. 1998

Synlett

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Treatment of unprotected pentitols and hexitols with RhH(PPh 3 ) 4 -benzalacetone system leads exclusively to glycono-1,4-lactones in 60-96% yield.The literature records a number of methods for the conversion of diols to lactones in yields varying from good to poor. These include: silver carbonate on Celite, 1 stoichiometric RuCl 2 (PPh 3 ) 3 in benzene, 2 CuSO 4 -KMnO 4 , 3 tetrapropylammonium perruthenate-4-methylmorpholine Noxide, 4 and catalytic hydrogen transfer (C.H.T) [benzalacetophenoneRuH 2 (PPh 3 ) 4 ] at 140°C. 5 To our knowledge, the latter is the only method which has been described to oxidize protected pentitols to afford the corresponding pentonolactones 6 and no method was applicable for the oxidation of unprotected itols to glyconolactones.In a previous paper we described the oxidation of protected or unprotected lactols to glycono-1,4-lactones, in mild conditions, by C.H.T with benzalacetone as hydrogen acceptor and RhH(PPh 3 ) 4 (hydridotetrakis triphenylphosphine rhodium I) as catalyst. 7 We report here the use of this system for the oxidation of unprotected itols to prepare glycono-1,4-lactones.As a matter of fact, we observed that treatment of meso erythritol 1 with RhH(PPh 3 ) 4 (0.2 eq) and benzalacetone (4 eq) in DMF for 3 hours at 60°C led to the racemic mixture of D,L-erythrono-1,4-lactone 2 in 95% isolated yield (Scheme 1). This method was also applied to other unprotected itols (tetritols, pentitols and hexitols) and efficiently yielded the glycono-1,4-lactones as shown in the Table. Scheme 1Pentitols and hexitols which have a plane of symmetry, for example meso erythritol 1, D-xylitol 8, D-galactitol 18 or a C-2 symmetry axis, such as D-threitol 3 or D-mannitol 13 led, with good yields, to the corresponding lactone obtained in a racemic mixture.Only one exception was observed when D-ribitol 5, having a plane of symmetry, was oxidized with 0.2 eq of catalyst and 4 eq of benzalacetone at 60°C for 5 hours. D,L-Ribono-1,4-lactone 6 and D,Larabinono-1,4-lactones 7 were isolated in 47% and 18% yield respectively. Similar epimerisation at C-2 was already observed in the oxidation of 2-acetamido-2-deoxy-D-mannopyranose with the same oxidizing system. 8When the oxidation of D-ribitol was performed at 80°C with 0.4 eq of RhH(PPh 3 ) 4 the overall yield increased to 94% but the ratio 6/7 remained equal to 2.5:1.The oxidation of L-arabinitol which has no symmetry led to the two expected L-arabinono-1,4-lactone 11 and L-lyxono-1,4-lactone 12 in 72% overall yield and in ratio 11/12=1.25:1.As explained in Scheme 2, after an oxidation at C-1 of L-arabinitol, the L-arabinopyranose or furanose formed was oxidized to give the Larabinono-1,4-lactone 11. The rare L-lyxono-1,4-lactone 12 is obtained via the L-lyxose resulting from the oxidation at the C-5 of the starting itol.Downloaded by: University of Illinois. Copyrighted material.

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Section: Letters Synlettmentioning

confidence: 98%

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

Isaac¹,

Aizel²,

Stasik³

et al. 1998

Synlett

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“…This was followed by a series of reports involving transition metal catalyzed oxidative esterification of alcohols to give dimerice sters. [26][27][28][29] Oxidation of benzylic alcohols was difficult since they tend to oxidize to benzaldehydes and the aliphatic alcohols to dimeric esters. Lei and co-workersa chieved dimeric esterification of benzyla lcohols using Pd in the absence of other aliphatic alcohol.…”

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confidence: 99%

Pd‐Colloids‐Catalyzed/Ag₂O‐Oxidized General and Selective Esterification of Benzylic Alcohols

Sable

Shah

Sharma

et al. 2019

Chemistry An Asian Journal

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“…The authors propose a catalytic cycle that starts from a resting state in which two aromatic aldehyde molecules coordinate to the Ni 0 center in h 2 fashion. [19] After the exchange of one of the coordinated aldehydes for an aliphatic aldehyde, a nickelacycle reversibly forms. [20] Subsequently, a nickel hydride species forms through b-hydride elimination, which reductively eliminates the ester product (Scheme 4).…”

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confidence: 99%

Selective Crossed‐Tishchenko Reaction—A Waste‐Free Synthesis of Benzyl Esters

Dzik

Gooßen

2011

Angew Chem Int Ed

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Homomolecular esterification of aldehydes catalyzed by hydridotetrakis(triphenylphosphine)rhodium(I)

Cited by 21 publications

References 18 publications

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

Pd‐Colloids‐Catalyzed/Ag₂O‐Oxidized General and Selective Esterification of Benzylic Alcohols

Selective Crossed‐Tishchenko Reaction—A Waste‐Free Synthesis of Benzyl Esters

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Homomolecular esterification of aldehydes catalyzed by hydridotetrakis(triphenylphosphine)rhodium(I)

Cited by 21 publications

References 18 publications

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh3)4-Benzalacetone System

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh3)4-Benzalacetone System

Pd‐Colloids‐Catalyzed/Ag2O‐Oxidized General and Selective Esterification of Benzylic Alcohols

Selective Crossed‐Tishchenko Reaction—A Waste‐Free Synthesis of Benzyl Esters

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A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

Pd‐Colloids‐Catalyzed/Ag₂O‐Oxidized General and Selective Esterification of Benzylic Alcohols