Review: Epoxidations of Alkenes with H2O2

[Rhodium]

Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide (Review)
Benjamin S. Lane and Kevin Burgess

Chem. Rev. 103(7) pp 2457 - 2474 (2003)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/metal-catalyzed.h2o2.epoxidation.review.pdf)
DOI:

10.1021/cr020471z

Introduction

Hydrogen peroxide is probably the best terminal oxidant after dioxygen with respect to environmental and economic considerations. Indeed, in certain circumstances, it is better than oxygen insofar as O₂/organic mixtures can sometimes spontaneously ignite. As a result, epoxidation systems that use hydrogen peroxide in conjunction with catalytic amounts of cheap, relatively nontoxic metals are potentially viable for large-scale production of inexpensive products, and for specialized applications in development, process, and research. The literature in this area is extensive and difficult to segregate into sharply delineated categories, but a fair way to attempt this is according to the catalyst precursors: "heterogeneous", "soluble metal oxides", and "homogeneous coordination complexes". Organic catalysts designed for asymmetric epoxidation may also function with hydrogen peroxide as a terminal oxidant, but they are beyond the scope of this review. The focus of this review is methods for the production of fine chemicals, but heterogeneous systems (more suitable for production of chemical commodities) are outlined for completeness.

[GC_MS]

Thanks for the review, Rh. It was a nice read.

Among all things I have read in the review, there was one chapter which asked for more attention than the others, viz. "4.2 Simple metal salts". It mentions that (p 2642) [...] Bicarbonate is an essential component in this transformation. It forms peroxymoncarbonate ion, HCO₄^-, in this system; the presence of the intermediate was observed using NMR on mixing hydrogen peroxide and HCO₃^-. Such equilibria had previously been observed by Richardson et al. for formation of HCO₄^- from hydrogen peroxide and bicarbonate in other solvents ¹¹⁷, and HCO₄^- without metal was found to be a moderately active epoxidizing agent in aqueous acetonitrile ¹¹⁸.[...]

Peroxymonocarbonate? ... Sodium percarbonate!  

http://www.scienceinthebox.com/en_UK/glossary/ingredientsafetyconsideration/percarbonate.shtml

http://www.solvayinterox.com/pcs.htm

I don't think I am unrealistic if I say that SPC - which even most Stimulant forum dwellers can find out to be OTC - might have something to offer us. Maybe a spoontip of the right catalyzing salt and SPC, and there might be no more need for HCOOH/H2O2, or AcOH/H2O2. Who knows...   . SPC is rather useful substance...

Post 377353

(GC_MS: "Sodium percarbonate and the Dakin reaction", Novel Discourse).

If somebee has access to JACS, would (s)he be so kind to check out references 116 through 119 (from the review), and post them if they are interesting?

[Rhodium]

A Cheap, Catalytic, Scalable, and Environmentally Benign Method for Alkene Epoxidations
Benjamin S. Lane and Kevin Burgess

J. Am. Chem. Soc. 123(12), 2933-2934 (2001)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.h2o2-mnso4.pdf)
DOI:

10.1021/ja004000a

Bicarbonate Activation of Hydrogen Peroxide: Oxidation of Sulfides by Peroxymonocarbonate
David E. Richardson, Huirong Yao, Karen M. Frank, and Deon A. Bennett

J. Am. Chem. Soc. 122(, 1729-1739 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/peroxymonocarbonate.pdf)
DOI:

10.1021/ja9927467

Epoxidation of Alkenes with Bicarbonate-Activated Hydrogen Peroxide
Huirong Yao and David E. Richardson

J. Am. Chem. Soc. 122(13), 3220-3221 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.bicarbonate-activated.h2o2.pdf)
DOI:

10.1021/ja993935s

Manganese-Catalyzed Epoxidations of Alkenes in Bicarbonate Solutions
Lane, B. S.; Vogt, M.; DeRose, V. J.; Burgess, K.;

J. Am. Chem. Soc. 124(40), 11946-11954 (2002)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.h2o2-mn-hco3.art.pdf)
DOI:

10.1021/ja025956j

Supplementary Information

(http://pubs.acs.org/subscribe/journals/jacsat/suppinfo/124/i40/ja025956j/ja025956j_s1.pdf)

[Rhodium]

These epoxidations, especially the last one, shows a lot of promise for our purposes - styrene being epoxidized in close to quantitative yield using aqueous bicarbonate and hydrogen peroxide with a little MnSO₄ as catalyst, which in turn is easily made from KMnO₄, just substitute the acetic acid with H₂SO₄ in my archived preparation of

manganous acetate

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/manganous.acetate.html). For the water-insoluble alkenes they use an organic co-solvent (DMF/MeCN/tBuOH) but isopropanol will probably also do, as the solvent is not participating in the reaction.



Possibly the reaction can be performed in a dual-phase setup, with the alkene in a DCM phase and the inorganics in an aqueous phase if a PTC is added - the great thing about the DCM being that it will automatically act as a heatsink, carrying away the heat from the exothermic reaction by boiling, thus keeping the reaction relatively cool even if the hydrogen peroxide is added relatively quickly (and not over 36h as they currently do on a full molar scale).

[Rhodium]

GC_MS - as you are so interested in percarbonate and epoxidations, do you have these articles?

Sodium Percarbonate (SPC) As A Hydrogen Peroxide Source For Organic Synthesis
Chem. Lett. 665-666 (1986)

Abstract: Sodium percarbonate (SPC) is an inexpensive, stable, safe and commercially available material which may be used as a hydrogen peroxide source for organic synthesis. Epoxidation, amine and sulfide oxidation reactions were simply performed with the solid reagent in moderate to excellent yield.

Sodium Perborate and Sodium Percarbonate in Organic Synthesis
Synthesis 1325-1347 (1995)

Abstract: This article reviews the oxidation of organic compounds carried out with either sodium perborate or sodium percarbonate as an oxygen source. Special attention is drawn to the differences in results provided by these two oxidants and to the influence of experimental conditions.

Sodium perborate and sodium percarbonate: further applications in organic synthesis
Alexander McKillop and William R. Sanderson 
J. Chem. Soc., Perkin Trans. 1, 2000, (4), 471 - 476 (Free access!)
DOI:

10.1039/a804579h

Abstract: Review of the literature covering the years 1995 to 1998.

[GC_MS]

I don't have the Chem Lett reference, but it is not that hard to acquire.

If you would have read the Addendum during correction from the Synthesis article, you would have found an equally interesting sodium percarbonate (SPC) / sodium perborate (SPB) review:

A McKillop, W R Sanderson. Sodium perborate and sodium percarbonate: cheap, safe and versatile oxidising agents for organic synthesis. Tetrahedron 51(22) (1995) 6145-6166. DOI:

10.1016/0040-4020(95)00304-Q

This review is complementary to the one published in Synthesis, and for sure is a must-read as well.

My interest was usually in SPB, and not SPC, because it was easier to get this compound in smaller quantities. I was unable to locate a company which wanted to deliver me less than 1 m³ SPC, or didn't make a 100x profit on the substane.

Useful SPB references in my collection:

1. Alexander McKillop, J A Tarbin. Functional group oxidation using sodium perborate. Tetrahedron 43( (1987) 1753-1758. DOI:

10.1016/S0040-4020(01)81484-8

Abstract - Sodium perborate in acetic acid is an effective reagent for the oxidation of anilines to nitroarenes and of sulphides to either sulphoxides or sulphones. it is also an excellent reagent for the oxidative deprotection of ketone dimethylhydrazones. Baeyer-Villiger oxidation of ketones can be carried out with sodium perborate in either trifluoroacetic acid or acetic acid/trifluoroacetic acid mixtures, and hydroquinones and certain highly substituted phenols are smoothly converted into quinones.



2. Alexander McKillop, Duncan Kemp. Further functional group oxidations using sodium perborate. Tetrahedron 45(11) (1989) 3299-3306. DOI:

10.1016/S0040-4020(01)81008-5

Abstract - Sodium perborate in acetic acid is an effective reagent for the oxidation of aromatic aldehydes to carboxylic acids, iodoarenes to (diacetoxyiodo)arenes, azines to N-oxides, and various types of sulphur heterocycles to S,S-dioxides. Nitriles are unaffected by the reagent in acetic acid, but undergo smooth dehydration to amides when aqueous methanol is employed as solvent.



3. Amalendu Banerjee, Banasri Hazra, Atashi Bhattacharya, Santanu Banerjee, Gopal C Banerjee, Saumitra Sengupta. Novel application of sodium perborate to the oxidation of aromatic aldehydes, ?-hydroxycarboxylic acids, 1,2-diketones, ?-hydroxyketones, 1,2-diols and some unsaturated compounds. Synthesis (1989) 765-766.

Abstract - Sodium perborate in acetic acid at 95°C oxidizes aromatic aldehydes, ?-hydroxycarboxylic acids, 1,2-diketones, benzoin, 1,2-diols and some unsaturated compounds.



4. Gaoyang Xie, Linxiao Xu, Jun Hu, Shiming Ma, Wei Hou, Fenggang Tao. Sodium perborate oxidations of cyclic and acyclic alkenes to oxiranes or vicinal acetoxy alcohols. Tetrahedron Letters 29(24) (1988) 2967-2968. DOI:

10.1016/0040-4039(88)85059-7

Abstract - Under different reaction conditions, sodium perborate/acetic anhydride oxidized alkenes into oxiranes or vicinal acetoxy alcohols in good yields.



5. Pakawan Nongkunsarn, Chistopher A Ramsden. Oxidative rearrangement of imines to formamides using sodium perborate. Tetrahedron 53(10) (1997) 3805-3830. DOI:

S0040-4020(97)00101-4

6. Didier Roche, Kapa Prasad, Oljan Repic, Thomas J Blacklock. Mild and regioselective oxidative bromination of anilines using potassium bromide and sodium perborate. Tetrahedron Letters 41 (2000) 2083-2085. DOI:

10.1016/S0040-4039(00)00119-2

Abstract - The selective monobromination of various deactivated anilines using potassium bromide and sodium perborate as oxidant has been achieved. The use of ammonium molybdate as catalyst accelerates the rate of reaction but is not essential to obtain good yields and high selectivities.



7. G W Kabalka, K Yang, N K Reddy, C Narayana. Bromination of alkenes using a mixture of sodium bromide and sodium perborate. Synthetic Communications 28(5) (1998) 925-929.

Abstract - Bromination of alkenes with sodium bromide in the presence sodium perborate provides a simple, high yield route to dibromoalkanes.



8. B P Bandgar, Miss Neeta J Nigal. Regioselective catalytic halogenation of aromatic substrates. Synthetic Communications 28(17) (1998) 3225-3229.

Abstract - Regioselective chlorination and bromination of some aromatic substances have been carried out using KCl and KBr in presence of sodium perborate as an oxidant and sodium metavanadate, sodium tungstate, ammonium metavanadate and ammonium molybdate as efficient catalysts. This environmentally friendly catalytic halogenation method gave good yields of products under mild conditions.



Except for the McKillop review and the imine>formamide rearrangement article, all articles can be req'd.

Some notes: The Kabalka article can be applied on propenylbenzenes to yield their dibromo derivatives (tested in the lab). I tried a iodination as well, but the end product was not purified nor analysed. However, upon addition of KI to the acetic acid/SPB mixture, there was an immediate formation of I2 (colour) and heat.
The Xie article has been evaluated a loooong time ago (before I found this board) and seems to work as well. I used Ac2O as reactant/solvent though, so I don't know how many bees are waiting for this adaptations. Reaction was over very quickly though. The method is solvent sensitive. DCM, for instance, has been tested and failed. Usually, acetic acid or acetic anhydride (or trifluoro analogues) are involved.

[Rhodium]

Here is the review from Tetrahedron. I didn't download the imine to formamide article, as it only concerned aromatic imines, and used trifluoroacetic acid as solvent.

Sodium perborate and sodium percarbonate: cheap, safe and versatile oxidising agents for organic synthesis. (Review)
A McKillop, W R Sanderson

Tetrahedron 51(22), 6145-6166 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/perborate-percarbonate.review.pdf)
DOI:

10.1016/0040-4020(95)00304-Q

[Rhodium]

As mentioned in

Post 446838

(GC_MS: "SPC/SPB", Novel Discourse):

Sodium perborate oxidations of cyclic and acyclic alkenes to oxiranes or vicinal acetoxy alcohols
Gaoyang Xie, Linxiao Xu, Jun Hu, Shiming Ma, Wei Hou, Fenggang Tao

Tetrahedron Letters 29(24), 2967-2968 (1988)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/perborate-epoxidation.pdf)
DOI:

10.1016/0040-4039(88)85059-7

Abstract

Under different reaction conditions, sodium perborate/acetic anhydride oxidized alkenes into oxiranes or vicinal acetoxy alcohols in good yields.

[GC_MS]

In

Post 446630 (missing)

(GC_MS: "SPC alkene oxidation", Novel Discourse), they didn't use solely SPC but also urea-hydrogen peroxide for alkene epoxidation purposes. Here is an article describing the synthesis of urea.H₂O₂.

G S Patil, G Nagendrappa. Epoxidation of cyclic vinylsilanes by urea-hydrogen peroxide complex.

Synthetic Communications 32(17) (2002) 2677-2681.

(https://www.thevespiary.org/rhodium/Rhodium/djvu/patil.djvu)
DOI:

10.1081/SCC-120006032

[...]

Preparation of urea-hydrogen peroxide complex (UHP)

Urea (65 g, 1.08 mol) was dissolved in 100 mL water of 30% w/v of H₂O₂ (0.88 mol) by warming to 40°C on a water bath. The resultant clear solution was cooled to 5-10°C for 30 min, when white crystals of UHP precipitated, which were filtered and air dried overnight. The complex was further dried oon P₂O₅ in a vacuum desiccator and stored in a refrigerator; yield, 34 g (41% based on H₂O₂ used); mp 90-92°C (Lit mp 90-93°C). The dry UHP complex was found to be >98.5% pure on the basis of molar ration of H₂O₂ and urea as estimated by iodimetric titration method using standard sodium thiosulfate solution.


And yes, the SPC epoxidation method is being tested   .

[Vitus_Verdegast]

The Urea-Hydrogen Peroxide Complex: Solid-State Oxidative Protocols for Hydroxylated Aldehydes and Ketones (Dakin Reaction), Nitriles, Sulfides, and Nitrogen Heterocycles.
Varma, Rajender S.; Naicker, Kannan P.
Organic Letters  (1999),  1(2),  189-191
DOI:

10.1021/ol990522n

CAN 131:102060, AN 1999:334353

An efficient solid-state oxidn. of org. mols. is described using a stable, inexpensive, and easily handled reagent, the urea-H2O2 adduct.  The generality of the reaction was demonstrated in oxidn. of several mols., hydroxylated aldehydes and ketones (to hydroxylated phenols), sulfides (to sulfoxides and sulfones), nitriles (to amides), and N heterocycles (to N-oxides). 



Asymmetric epoxidation of enones employing polymeric a-amino acids in non-aqueous media.
Bentley, Paul A.; Bergeron, Sophie; Cappi, Michael W.; Hibbs, David E.; Hursthouse, Michael B.; Nugent, Thomas C.; Pulido, Rosalino; Roberts, Stanley M.; Wu, L. Eduardo.
Chemical Communications (Cambridge)  (1997),   (,  739-740
CAN 127:34072, AN 1997:330663

Urea-hydrogen peroxide complex in an org. solvent and in the presence of DBU and poly-(L)-leucine causes rapid asym. epoxidn. of the enones R1CH:CHCOR2 (R1 = R2 = Ph; R1 = CH:CHPh, R2 = 2-naphthyl; R1 = Ph, R2 = Me2CH, Me). 



A very simple oxidation of olefins and ketones with UHP [urea-hydrogen peroxide] - maleic anhydride.
Astudillo, Luis; Galindo, Antonio; Gonzalez, Antonio G.; Mansilla, Horacio.
Heterocycles  (1993),  36(5),  1075-80
CAN 119:202722, AN 1993:602722

The oxidn. of olefins and ketones to oxiranes and esters, resp., is carried out with the UHP (urea-hydrogen peroxide complex)-maleic anhydride system in a mild and very simple procedure.  Byproducts urea and maleic acid are readily removed by filtration. 



Enantioselective epoxidation of non-functionalized alkenes using a urea-hydrogen peroxide oxidant and a dimeric homochiral Mn(III)-Schiff base complex catalyst.
Kureshy, Rukhsana I.; Khan, Noor-ul H.; Abdi, Sayed H. R.; Patel, Sunil T.; Jasra, Raksh V.
Tetrahedron: Asymmetry  (2001),  12(3),  433-437
DOI:

10.1016/S0957-4166(01)00057-X

CAN 135:107192, AN 2001:259373

The catalytic enantioselective epoxidn. of chromenes, indene and styrene using a urea-hydrogen peroxide adduct as an oxidizing agent and a novel dimeric homochiral Mn(III)-Schiff base catalyst has been investigated in the presence of carboxylate salts and nitrogen and oxygen coordinating co-catalysts.  Conversions of >99% were obtained with all alkenes except styrene.  Abs. chiral induction, as detd. by 1H NMR using the chiral shift reagent (+)-Eu(hfc)3, was obtained in the case of nitro- and cyanochromene.  The catalyst could be re-used for up to five cycles with some loss of activity due to degrdn. of the catalyst under epoxidn. conditions with retention of e.e.'s.

[Vitus_Verdegast]

Oxidation Reactions Using Urea-Hydrogen Peroxide; A Safe Alternative to Anhydrous Hydrogen Peroxide

Mark S. Cooper*, Harry Heaney, Amanda J. Newbold, William R. Sanderson

*Department of Chemistry, Loughborough University of Technology, Leicestershire, LE11 3TU, England
 
Synlett (1990) p. 533-535

http://www.geocities.com/phorkys_hecate/0-01210773019689-1077302816.pdf

DOI:

10.1055/s-1990-21156

Abstract
Urea-hydrogen peroxide (UHP) alone or in combination with carboxylic anhydrides has been shown to serve as a valuable alternative to anhydrous hydrogen peroxide: the range of substrates oxidised include alkenes (epoxidation), ketones (Baeyer-Villiger reaction), sulphides (to sulphones), nitrogen heterocycles (to N-oxides), and aromatic hydrocarbons (to phenols).

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I'd be glad to type the article up if someone wants, but I can't now as I have very little free time for the moment

[Rhodium]

A simple and efficient method for epoxidation of terminal alkenes
C. Copéret, H. Adolfsson and K. B. Sharpless

J. Chem. Soc. Chem. Commun. 1565-1566 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/terminal.epoxidation.mto.pdf)

Abstract
The use of a catalytic amount of 3-cyanopyridine in the methyltrioxorhenium catalysed epoxidation of terminal alkenes with aqueous hydrogen peroxide speeds turnover, which results in the formation of many functionalized epoxides in high yields.

Representative procedure for the epoxidation of terminal alkenes:

A mixture of dec-1-ene (28.0 g, 200 mmol), 3-cyanopyridine (2.08 g, 20 mmol) and MTO (249 mg, 1 mmol) in CH₂Cl₂ (120 ml) was treated with 40 ml of 30% oxygen evolution ceased (1 h). Following phase separation, the water layer was extracted with CH₂Cl₂, the combined organic layers were dried over Na₂SO₄ and concentrated to an oil. Hexane was added to this crude product, and the resulting white precipitate was removed by filtration. The filtrate was concentrated, and the crude colourless oil was distilled to yield 31.4 g of decene oxide (94% yield, 96.5% purity).

In summary, a remarkable, albeit poorly understood, beneficial effect of 3-cyanopyridine on MTO-catalysed epoxidations of terminal alkenes has been established. For this challenging class of substrates, this method of epoxidation could prove to be one of the most convenient because:

(i) it shows good functional group compatibility (wide scope)
(ii) it is mild (i.e. neutral conditions, room temperature)
(iii) it uses a readily available, safe and environmentally friendly oxidizing agent (30% aqueous H₂O₂)
(iv) it is easy to perform on the scales common (1 to 200 mmol) in the laboratory (no tedious work-up, no by-products).

[Rhodium]

Highly selective epoxidation of alkenes and styrenes with H₂O₂ and manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane
Dirk De Vos and Thomas Bein

JCS Chem. Commun. 917-918 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/www.rhodium.ws/pdf/epoxidation-triazacyclononane.pdf)

Abstract
In acetone and at subambient temperatures, manganese complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane catalyse the selective oxidation of many alkenes and styrenes to epoxides with an efficient use of H₂O₂; the regio- and chemo-selectivity resemble those of manganese–porphyrin catalysts.

[Rhodium]

Manganese catalysts in homogeneous oxidation reactions
Jelle Brinksma,

Thesis, Univ. Groningen (2002)

(http://www.ub.rug.nl/eldoc/dis/science/j.brinksma)

Table Of Contents

• Introduction Oxidation Catalysis
• Manganese Complexes as Homogeneous Epoxidation Catalysts
• In Situ Prepared Manganese Complexes as Homogeneous Catalysts for Epoxidation Reactions with Hydrogen Peroxide
• Homogeneous cis-Dihydroxylation and Epoxidation of Olefins with High Hydrogen Peroxide Efficiency by Mixed Manganese/Activated Carbonyl Systems
• Manganese Catalysts for Alcohol Oxidation
• New Ligands for Manganese Catalysed Selective Oxidation of Sulfides to Sulfoxides with Hydrogen Peroxide
• Conclusions and Future Prospects