1,2- Versus 1,4-Asymmetric Reduction of Ketones

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• 关键词：Asymmetric catalysis ; Carbonyl compounds ; Copper ; Enantioselectivity ; Regioselectivity ; Silanes
• 刊名：Topics in Organometallic Chemistry
• 出版年：2016
• 出版时间：2016
• 年：2016
• 卷：58
• 期：1
• 页码：207-220
• 全文大小：579 KB
• 参考文献：1.Hudlicky M (1984) Reductions in organic chemistry. Ellis Horwood, Chichester
  2.Rendler S, Oestreich M (2007) Polishing a diamond in the rough: “Cu–H” catalysis with silanes. Angew Chem Int Ed 46:498–504. doi:10.​1002/​anie.​200602668 CrossRef
  3.Deutsch C, Krause N, Lipshutz BH (2008) CuH-catalyzed reactions. Chem Rev 108:2916–2927. doi:10.​1021/​cr0684321 CrossRef
  4.Lipshutz B (2009) Rediscovering organocopper chemistry through copper hydride. It’s all about the ligand. Synlett 2009:509–524. doi:10.​1055/​s-0028-1087923 CrossRef
  5.Moritani Y, Appella DH, Jurkauskas V, Buchwald SL (2000) Synthesis of β-alkyl cyclopentanones in high enantiomeric excess via copper-catalyzed asymmetric conjugate reduction. J Am Chem Soc 122:6797–6798. doi:10.​1021/​ja0009525 CrossRef
  6.Lipshutz BH, Servesko JM (2003) CuH-catalyzed asymmetric conjugate reductions of acyclic enones. Angew Chem Int Ed 42:4789–4792. doi:10.​1002/​anie.​200352313 CrossRef
  7.Lipshutz BH, Servesko JM, Petersen TB, Papa PP, Lover AA (2004) Asymmetric 1,4-reductions of hindered β-substituted cycloalkenones using catalytic SEGPHOS–ligated CuH. Org Lett 6:1273–1275. doi:10.​1021/​ol0400185 CrossRef
  8.Lipshutz BH, Amorelli B, Unger JB (2008) CuH-catalyzed enantioselective intramolecular reductive aldol reactions generating three new contiguous asymmetric stereocenters. J Am Chem Soc 130:14378–14379. doi:10.​1021/​ja8045475 CrossRef
  9.Yun J, Buchwald SL (2001) One-pot synthesis of enantiomerically enriched 2,3-disubstituted cyclopentanones via copper-catalyzed 1,4-reduction and alkylation. Org Lett 3:1129–1131. doi:10.​1021/​ol015577f CrossRef
  10.Chae J, Yun J, Buchwald SL (2004) One-pot sequential Cu-catalyzed reduction and Pd-catalyzed arylation of silyl enol ethers. Org Lett 6:4809–4812. doi:10.​1021/​ol048313c CrossRef
  11.Liu H, Zhang W, He L, Luo M, Qin S (2014) Computational investigations on the phosphine-ligated CuH-catalyzed conjugate reduction of α-β unsaturated ketones: regioselectivity and stereoselectivity. RSC Adv 4:5726. doi:10.​1039/​c3ra44015j CrossRef
  12.Chen JX, Daeuble JF, Brestensky DM, Stryker JM (2000) Highly chemoselective catalytic hydrogenation of unsaturated ketones and aldehydes to unsaturated alcohols using phosphine-stabilized copper (I) hydride …. Tetrahedron 56:2153–2166. doi:10.​1016/​s0040-4020(99)01098-4 CrossRef
  13.Moser R, Bošković ZV, Crowe CS, Lipshutz BH (2010) CuH-catalyzed enantioselective 1,2-reductions of α, β-unsaturated ketones. J Am Chem Soc 132:7852–7853. doi:10.​1021/​ja102689e CrossRef
  14.Junge K, Wendt B, Addis D, Zhou S, Das S, Beller M (2010) Copper-catalyzed enantioselective hydrosilylation of ketones by using monodentate binaphthophosphepine ligands. Chem Eur J 16:68–73. doi:10.​1002/​chem.​200902442 CrossRef
  15.Voigtritter KR, Isley NA, Moser R, Aue DH, Lipshutz BH (2012) Regioselective reductions of β, β-disubstituted enones catalyzed by nonracemically ligated copper hydride. Tetrahedron 68:3410–3416. doi:10.​1016/​j.​tet.​2011.​10.​056 CrossRef
  16.Brunner H, Miehling W (1984) Asymmetrische katalysen: XXII. Enantioselektive hydrosilylierung von ketonen mit CuI-katalysatoren. J Organomet Chem 275:c17–c21. doi:10.​1016/​0022-328X(84)85066-4 CrossRef
  17.Lipshutz BH, Noson K, Chrisman W (2001) Ligand-accelerated, copper-catalyzed asymmetric hydrosilylations of aryl ketones. J Am Chem Soc 123:12917–12918. doi:10.​1021/​ja011529e CrossRef
  18.Wu J, Chan ASC (2006) P-Phos: a family of versatile and effective atropisomeric dipyridylphosphine ligands in asymmetric catalysis. Acc Chem Res 39:711–720. doi:10.​1021/​ar0680015 CrossRef
  19.Wu J, Ji J-X, Chan ASC (2005) A remarkably effective copper(II)-dipyridylphosphine catalyst system for the asymmetric hydrosilylation of ketones in air. Proc Natl Acad Sci 102:3570–3575. doi:10.​1073/​pnas.​0409043102 CrossRef
  20.Zhang X-C, Wu F-F, Li S, Zhou J-N, Wu J, Li N, Fang W, Lam KH, Chan ASC (2011) Copper-dipyridylphosphine-polymethylhydrosiloxane: a practical and effective system for the asymmetric catalytic hydrosilylation of ketones. Adv Synth Catal 353:1457–1462. doi:10.​1002/​adsc.​201100105 CrossRef
  21.Yu F, Zhou J-N, Zhang X-C, Sui Y-Z, Wu F-F, Xie L-J, Chan ASC, Wu J (2011) Copper(II)-catalyzed hydrosilylation of ketones using chiral dipyridylphosphane ligands: highly enantioselective synthesis of valuable alcohols. Chem Eur J 17:14234–14240. doi:10.​1002/​chem.​201102157 CrossRef
  22.Zhou J-N, Fang Q, Hu Y-H, Yang L-Y, Wu F-F, Xie L-J, Wu J, Li S (2014) Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine. Org Biomol Chem 12:1009–1017. doi:10.​1039/​c3ob42214c CrossRef
  23.Qi S-B, Li M, Li S, Zhou J-N, Wu J-W, Yu F, Zhang X-C, Chan ASC, Wu J (2013) Copper-dipyridylphosphine-catalyzed hydrosilylation: enantioselective synthesis of aryl- and heteroarylcycloalkyl alcohols. Org Biomol Chem 11:929–937. doi:10.​1039/​C2OB27040D CrossRef
  24.Schmidt F, Stemmler RT, Rudolph J, Bolm C (2006) Catalytic asymmetric approaches towards enantiomerically enriched diarylmethanols and diarylmethylamines. Chem Soc Rev 35:1–17. doi:10.​1039/​b600091f CrossRef
  25.Lee C-T, Lipshutz BH (2008) Nonracemic diarylmethanols from CuH-catalyzed hydrosilylation of diaryl ketones. Org Lett 10:4187–4190. doi:10.​1021/​ol801590j CrossRef
  26.Sui Y-Z, Zhang X-C, Wu J-W, Li S, Zhou J-N, Li M, Fang W, Chan ASC, Wu J (2012) Cu II-catalyzed asymmetric hydrosilylation of diaryl- and aryl heteroaryl ketones: application in the enantioselective synthesis of orphenadrine and neobenodine. Chem Eur J 18:7486–7492. doi:10.​1002/​chem.​201200379 CrossRef
  
• 作者单位：Andrei V. Malkov (14)
  Kurt Lawson (14)
  
  14. Department of Chemistry, Loughborough University, Loughborough, Leicestershire, LE11 3TU, UK
  
• 丛书名：Progress in Enantioselective Cu(I)-catalyzed Formation of Stereogenic Centers
• ISBN：978-3-319-33414-1
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Organometallic Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1616-8534
• 卷排序：58

文摘

Reduction of α,β-unsaturated ketones generally can give rise to a variety of products, of which chiral allylic alcohols (1,2-reduction) and saturated ketones (1,4-reduction) are the most useful from the synthetic point of view. With the appropriate substitution pattern these processes generate new stereogenic centres, where copper hydride coordinated to chiral ligand provided useful level of enantioselectivity. Attractiveness of the catalytic systems based on Cu(I) owes it to their high catalytic activity, low cost and ability to employ hydrogen or ubiquitous hydrosilanes as stoichiometric reducing reagents. This overview is focused on the efforts directed at developing and refining practical methods to tackle the issues of regio- and enantioselectivity with a particular focus on selective 1,2- and 1,4-manifolds, it mostly covers research published in 2010–2015 referring to earlier works for maintaining continuity.