Organic & Biomolecular Chemistry
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Organic & Biomolecular Chemistry Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/obc Page 1 of 55 Organic & Biomolecular Chemistry Synthetic applications of hypophosphite derivatives in reduction Carole Guyon, Estelle Métay*, Florence Popowycz*, Marc Lemaire aEquipe Catalyse Synthèse Environnement, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR-CNRS 5246, Université de Lyon, Université Claude Bernard-Lyon 1, Bâtiment Curien, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne Cedex, France Tel: +33-(0)4 72 43 14 07 ; Fax: +33-(0)4 72 43 14 08; E-mail : [email protected] b Equipe Chimie Organique et Bioorganique, Institut de Chimie et Biochimie Moléculaires et Manuscript Supramoléculaires, UMR-CNRS 5246, Institut National des Sciences Appliquées (INSA Lyon), Bâtiment Jules Verne, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France Tel : +33-(0)4 72 43 82 21 Fax : +33-(0)4 72 43 88 96 E-mail : [email protected] Table of contents 1. Introduction ......................................................................................................................................................................... 2 Accepted 2. Hypophosphites and other phosphorus derivatives .............................................................................................................. 3 3. Cleavage of carbon-heteroatom single bonds ...................................................................................................................... 7 3.1. Dehalogenation reaction .......................................................................................................................................7 3.1.1. Dechlorination .......................................................................................................................................................... 7 3.1.2. Debromination ........................................................................................................................................................ 10 3.1.3. Deiodination............................................................................................................................................................ 11 3.2. C-O bond cleavage – Reductive cleavage of benzyl ether and benzyl carbonate ........................................................... 11 3.3. Se-Se bond cleavage ....................................................................................................................................................... 12 3.4. C-S and S-S bond cleavage ............................................................................................................................................. 13 3.5. Reductive C-N bond cleavage ........................................................................................................................................ 14 3.5.1. Reductive cleavage of benzyl amine and benzyl carbamate.................................................................................... 14 Chemistry 3.5.2. Hydro-dediazoniation ............................................................................................................................................. 15 4. Reduction of C-C multiple bonds ...................................................................................................................................... 16 4.1. Alkene reduction............................................................................................................................................................. 16 4.2. Alkyne reduction ............................................................................................................................................................ 20 4.2.1. To alkanes ............................................................................................................................................................... 20 4.2.2. To alkenes ............................................................................................................................................................... 21 4.2.3. Reductive decomplexation ...................................................................................................................................... 23 5. Reduction of C-heteroatom multiple bonds ....................................................................................................................... 24 5.1. Reduction of carbonyl derivatives .................................................................................................................................. 24 5.2. Reductive amination ....................................................................................................................................................... 26 5.3. Reduction of carboxylic acid derivatives ........................................................................................................................ 27 5.4. Reduction of nitriles ....................................................................................................................................................... 27 6. Deoxygenation .................................................................................................................................................................. 30 Biomolecular 6.1. Deoxygenation of carbon compounds............................................................................................................................. 30 & 6.1.1. Deoxygenation of phenols into arenes .................................................................................................................... 30 6.1.2. Radical deoxygenation ............................................................................................................................................ 32 6.1.3. Reduction of carbonyl derivatives to methylenes ................................................................................................... 34 6.2. Deoxygenation of sulfur compounds .............................................................................................................................. 36 6.3. Deoxygenation of nitrogen compounds .......................................................................................................................... 36 6.3.1. Reduction of nitro derivatives ................................................................................................................................. 36 6.3.1.1. Amine synthesis ........................................................................................................................................... 36 6.3.1.2. Hydroxylamine synthesis and Bamberger rearrangement ............................................................................ 39 6.3.1.3. Reduction of nitroalkenes ............................................................................................................................ 40 6.3.2. Reduction of oximes ............................................................................................................................................... 41 Organic 6.3.3. Reduction of N-oxides ............................................................................................................................................ 41 1 Organic & Biomolecular Chemistry Page 2 of 55 7. Conclusion......................................................................................................................................................................... 42 1. Introduction Catalytic hydrogenation and reduction using metal hydrides are two of the main reduction tools of modern organic chemistry. Catalytic hydrogenation 1 is often preferred for ecological and economic reasons; the amount of waste in that case produced is much lower (principles 2 and 8 of green chemistry). Nevertheless, the use of aluminum and boron hydrides is still very Manuscript important mainly because such reagents often allow better regio- and chemo-selectivity. On the contrary, enantioselectivity is generally obtained using hydrogenation with transition metal catalysts. 2 The development of aluminum and boron hydrides was one of the great successes in the chemistry of the second part of the 20 th century. 3 These hydrides are the subject of numerous Accepted books, chapters, reviews and are taught in both theoretical and practical courses in University and Chemistry Schools. 4 However, the search for more specific and efficient reagents for large scale industrial applications,