In organic chemistry, carbonyl allylation describes methods for adding an allyl anion to an aldehyde or ketone to produce a homoallylic alcohol.[1] The carbonyl allylation was first reported in 1876 by Alexander Zaitsev and employed an allylzinc reagent.[2]
In 1978, Hoffmann reported the first asymmetric carbonyl allylation using a chiral allylmetal reagent, an allylborane derived from camphor.[3][4] Such methods utilize preformed allyl metal reagents. The approach is well developed using allyl boranes[5]
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As illustrated by the Keck allylation,[6] catalytic enantioselective additions of achiral allylmetal reagents to carbonyl compounds also are possible by organostannane additions.[7]
Allylic boronate and -borane reagents have also been developed for enantioselective addition to carbonyls—in this class of reactions, the allylic boron reagent confers stereochemical control[5]
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Catalysisedit
In 1991, Yamamoto disclosed the first catalytic enantioselective method for carbonyl allylation, which employed a chiral boron Lewis acid-catalyst in combination with allyltrimethylsilane.[8] Numerous other catalytic enantioselective methods for carbonyl allylation followed.[9][6] Catalytic variants of the Nozaki-Hiyama-Kishi reaction represent an alternative method for asymmetric carbonyl allylation, but stoichiometric metallic reductants are required.[10]
Whereas the aforementioned asymmetric carbonyl allylations rely on preformed allylmetal reagents, the Krische allylation exploits allyl acetate for enantioselective carbonyl allylation.[11] Selected methods for asymmetric carbonyl allylation are summarized below.
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Use in total synthesisedit
Carbonyl allylation has been employed in the synthesis of polyketide natural products and other oxygenated molecules with a contiguous array of stereocenters. For example, allylstannanation of a threose-derived aldehyde affords the macrolide antascomicin B, which structurally resembles FK506 and rapamycin, and is a potent binder of FKBP12.[12] The Krische allylation was used to prepare the polyketide (+)-SCH 351448, a macrodiolide ionophore bearing 14 stereogenic centers.[13]
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Older primary literatureedit
Brown, Herbert C.; Jadhav, Prabhakar K. (April 1983). "Asymmetric carbon-carbon bond formation via .beta.-allyldiisopinocampheylborane. Simple synthesis of secondary homoallylic alcohols with excellent enantiomeric purities". Journal of the American Chemical Society. 105 (7): 2092–2093. doi:10.1021/ja00345a085. ISSN 0002-7863.
Hayashi, Tamio; Konishi, Mitsuo; Kumada, Makoto (1982-09-01). "Optically active allylsilanes. 2. High stereoselectivity in asymmetric reaction with aldehydes producing homoallylic alcohols". Journal of the American Chemical Society. 104 (18): 4963–4965. doi:10.1021/ja00382a046.
Roush, William R.; Walts, Alan E.; Hoong, Lee K. (1985-12-01). "Diastereo- and enantioselective aldehyde addition reactions of 2-allyl-1,3,2-dioxaborolane-4,5-dicarboxylic esters, a useful class of tartrate ester modified allylboronates". Journal of the American Chemical Society. 107 (26): 8186–8190. doi:10.1021/ja00312a062.
Brown, Herbert C.; Jadhav, Prabhakar K. (April 1983). "Asymmetric carbon-carbon bond formation via .beta.-allyldiisopinocampheylborane. Simple synthesis of secondary homoallylic alcohols with excellent enantiomeric purities". Journal of the American Chemical Society. 105 (7): 2092–2093. doi:10.1021/ja00345a085. ISSN 0002-7863.
Kinnaird, James W. A.; Ng, Pui Yee; Kubota, Katsumi; Wang, Xiaolun; Leighton, James L. (2002-07-01). "Strained Silacycles in Organic Synthesis: A New Reagent for the Enantioselective Allylation of Aldehydes". Journal of the American Chemical Society. 124 (27): 7920–7921. doi:10.1021/ja0264908. ISSN 0002-7863. PMID 12095334.
Short, Robert P.; Masamune, Satoru (March 1989). "Asymmetric allylboration with B-allyl-2-(trimethylsilyl)borolane". Journal of the American Chemical Society. 111 (5): 1892–1894. doi:10.1021/ja00187a061. ISSN 0002-7863.
Corey, E. J.; Yu, Chan Mo; Kim, Sung Soo (July 1989). "A practical and efficient method for enantioselective allylation of aldehydes". Journal of the American Chemical Society. 111 (14): 5495–5496. doi:10.1021/ja00196a082. ISSN 0002-7863.
Referencesedit
^Yus, Miguel; González-Gómez, José C.; Foubelo, Francisco (2011). "Catalytic Enantioselective Allylation of Carbonyl Compounds and Imines". Chemical Reviews. 111 (12): 7774–7854. doi:10.1021/cr1004474. PMID 21923136.
^Michael; Saytzeff, Alexander (1877). "Synthese des Allyldimethylcarbinols". Justus Liebigs Annalen der Chemie. 185 (2–3): 151–169. doi:10.1002/jlac.18771850204. ISSN 1099-0690.
^Herold, Thomas; Hoffmann, Reinhard W. (1978-10-01). "Enantioselective Synthesis of Homoallyl Alcohols via Chiral Allylboronic Esters". Angewandte Chemie International Edition in English. 17 (10): 768–769. doi:10.1002/anie.197807682.
^Hoffmann, Reinhard W.; Herold, Thomas (1981-01-01). "Stereoselektive Synthese von Alkoholen, VII1) Optisch aktive Homoallylalkohole durch Addition chiraler Boronsäureester an Aldehyde". Chemische Berichte. 114 (1): 375–383. doi:10.1002/cber.19811140139.
^ abDenmark, S. E.; Almstead, N. G. In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH: Weinheim, 2000; Chapter 10.
^ abKeck, Gary E.; Tarbet, Kenneth H.; Geraci, Leo S. (1993-09-01). "Catalytic asymmetric allylation of aldehydes". Journal of the American Chemical Society. 115 (18): 8467–8468. doi:10.1021/ja00071a074.
^Denmark, Scott E.; Fu, Jiping (2003-08-01). "Catalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones". Chemical Reviews. 103 (8): 2763–2794. doi:10.1021/cr020050h. ISSN 0009-2665. PMID 12914480.
^Costa, Anna Luisa; Piazza, Maria Giulia; Tagliavini, Emilio; Trombini, Claudio; Umani-Ronchi, Achille (1993-07-01). "Catalytic asymmetric synthesis of homoallylic alcohols". Journal of the American Chemical Society. 115 (15): 7001–7002. doi:10.1021/ja00068a079.
^Hargaden, Gráinne C.; Guiry, Patrick J. (2007-11-05). "The Development of the Asymmetric Nozaki–Hiyama–Kishi Reaction". Advanced Synthesis & Catalysis. 349 (16): 2407–2424. doi:10.1002/adsc.200700324.
^Kim, In Su; Ngai, Ming-Yu; Krische, Michael J. (2008-11-05). "Enantioselective Iridium-Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level via Transfer Hydrogenative Coupling of Allyl Acetate: Departure from Chirally Modified Allyl Metal Reagents in Carbonyl Addition". Journal of the American Chemical Society. 130 (44): 14891–14899. doi:10.1021/ja805722e. ISSN 0002-7863. PMC2890235. PMID 18841896.
^Brittain, Dominic E. A.; Griffiths-Jones, Charlotte M.; Linder, Michael R.; Smith, Martin D.; McCusker, Catherine; Barlow, Jaqueline S.; Akiyama, Ryo; Yasuda, Kosuke; Ley, Steven V. (2005). "Total Synthesis of Antascomicin B". Angewandte Chemie International Edition. 44 (18): 2732–2737. doi:10.1002/anie.200500174. ISSN 1521-3773. PMID 15806607.
^Wang, Gang; Krische, Michael J. (2016-07-06). "Total Synthesis of (+)-SCH 351448: Efficiency via Chemoselectivity and Redox-Economy Powered by Metal Catalysis". Journal of the American Chemical Society. 138 (26): 8088–8091. doi:10.1021/jacs.6b04917. ISSN 0002-7863. PMC4935581. PMID 27337561.
December 15, 2023
carbonyl, allylation, organic, chemistry, carbonyl, allylation, describes, methods, adding, allyl, anion, aldehyde, ketone, produce, homoallylic, alcohol, carbonyl, allylation, first, reported, 1876, alexander, zaitsev, employed, allylzinc, reagent, insert, ca. In organic chemistry carbonyl allylation describes methods for adding an allyl anion to an aldehyde or ketone to produce a homoallylic alcohol 1 The carbonyl allylation was first reported in 1876 by Alexander Zaitsev and employed an allylzinc reagent 2 insert a caption hereContents 1 Enantioselective versions 1 1 Catalysis 2 Use in total synthesis 3 Older primary literature 4 ReferencesEnantioselective versions editIn 1978 Hoffmann reported the first asymmetric carbonyl allylation using a chiral allylmetal reagent an allylborane derived from camphor 3 4 Such methods utilize preformed allyl metal reagents The approach is well developed using allyl boranes 5 13 nbsp As illustrated by the Keck allylation 6 catalytic enantioselective additions of achiral allylmetal reagents to carbonyl compounds also are possible by organostannane additions 7 Allylic boronate and borane reagents have also been developed for enantioselective addition to carbonyls in this class of reactions the allylic boron reagent confers stereochemical control 5 13 nbsp Catalysis edit In 1991 Yamamoto disclosed the first catalytic enantioselective method for carbonyl allylation which employed a chiral boron Lewis acid catalyst in combination with allyltrimethylsilane 8 Numerous other catalytic enantioselective methods for carbonyl allylation followed 9 6 Catalytic variants of the Nozaki Hiyama Kishi reaction represent an alternative method for asymmetric carbonyl allylation but stoichiometric metallic reductants are required 10 Whereas the aforementioned asymmetric carbonyl allylations rely on preformed allylmetal reagents the Krische allylation exploits allyl acetate for enantioselective carbonyl allylation 11 Selected methods for asymmetric carbonyl allylation are summarized below nbsp insert a caption hereUse in total synthesis editCarbonyl allylation has been employed in the synthesis of polyketide natural products and other oxygenated molecules with a contiguous array of stereocenters For example allylstannanation of a threose derived aldehyde affords the macrolide antascomicin B which structurally resembles FK506 and rapamycin and is a potent binder of FKBP12 12 The Krische allylation was used to prepare the polyketide SCH 351448 a macrodiolide ionophore bearing 14 stereogenic centers 13 nbsp insert a caption hereOlder primary literature editBrown Herbert C Jadhav Prabhakar K April 1983 Asymmetric carbon carbon bond formation via beta allyldiisopinocampheylborane Simple synthesis of secondary homoallylic alcohols with excellent enantiomeric purities Journal of the American Chemical Society 105 7 2092 2093 doi 10 1021 ja00345a085 ISSN 0002 7863 Hayashi Tamio Konishi Mitsuo Kumada Makoto 1982 09 01 Optically active allylsilanes 2 High stereoselectivity in asymmetric reaction with aldehydes producing homoallylic alcohols Journal of the American Chemical Society 104 18 4963 4965 doi 10 1021 ja00382a046 Roush William R Walts Alan E Hoong Lee K 1985 12 01 Diastereo and enantioselective aldehyde addition reactions of 2 allyl 1 3 2 dioxaborolane 4 5 dicarboxylic esters a useful class of tartrate ester modified allylboronates Journal of the American Chemical Society 107 26 8186 8190 doi 10 1021 ja00312a062 Brown Herbert C Jadhav Prabhakar K April 1983 Asymmetric carbon carbon bond formation via beta allyldiisopinocampheylborane Simple synthesis of secondary homoallylic alcohols with excellent enantiomeric purities Journal of the American Chemical Society 105 7 2092 2093 doi 10 1021 ja00345a085 ISSN 0002 7863 Kinnaird James W A Ng Pui Yee Kubota Katsumi Wang Xiaolun Leighton James L 2002 07 01 Strained Silacycles in Organic Synthesis A New Reagent for the Enantioselective Allylation of Aldehydes Journal of the American Chemical Society 124 27 7920 7921 doi 10 1021 ja0264908 ISSN 0002 7863 PMID 12095334 Short Robert P Masamune Satoru March 1989 Asymmetric allylboration with B allyl 2 trimethylsilyl borolane Journal of the American Chemical Society 111 5 1892 1894 doi 10 1021 ja00187a061 ISSN 0002 7863 Corey E J Yu Chan Mo Kim Sung Soo July 1989 A practical and efficient method for enantioselective allylation of aldehydes Journal of the American Chemical Society 111 14 5495 5496 doi 10 1021 ja00196a082 ISSN 0002 7863 References edit Yus Miguel Gonzalez Gomez Jose C Foubelo Francisco 2011 Catalytic Enantioselective Allylation of Carbonyl Compounds and Imines Chemical Reviews 111 12 7774 7854 doi 10 1021 cr1004474 PMID 21923136 Michael Saytzeff Alexander 1877 Synthese des Allyldimethylcarbinols Justus Liebigs Annalen der Chemie 185 2 3 151 169 doi 10 1002 jlac 18771850204 ISSN 1099 0690 Herold Thomas Hoffmann Reinhard W 1978 10 01 Enantioselective Synthesis of Homoallyl Alcohols via Chiral Allylboronic Esters Angewandte Chemie International Edition in English 17 10 768 769 doi 10 1002 anie 197807682 Hoffmann Reinhard W Herold Thomas 1981 01 01 Stereoselektive Synthese von Alkoholen VII1 Optisch aktive Homoallylalkohole durch Addition chiraler Boronsaureester an Aldehyde Chemische Berichte 114 1 375 383 doi 10 1002 cber 19811140139 a b Denmark S E Almstead N G In Modern Carbonyl Chemistry Otera J Ed Wiley VCH Weinheim 2000 Chapter 10 a b Keck Gary E Tarbet Kenneth H Geraci Leo S 1993 09 01 Catalytic asymmetric allylation of aldehydes Journal of the American Chemical Society 115 18 8467 8468 doi 10 1021 ja00071a074 Denmark Scott E Fu Jiping 2003 08 01 Catalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones Chemical Reviews 103 8 2763 2794 doi 10 1021 cr020050h ISSN 0009 2665 PMID 12914480 Furuta Kyoji Mouri Makoto Yamamoto Hisashi 1991 01 01 Chiral Acyloxy borane Catalyzed Asymmetric Allylation of Aldehydes Synlett 1991 8 561 562 doi 10 1055 s 1991 20797 Costa Anna Luisa Piazza Maria Giulia Tagliavini Emilio Trombini Claudio Umani Ronchi Achille 1993 07 01 Catalytic asymmetric synthesis of homoallylic alcohols Journal of the American Chemical Society 115 15 7001 7002 doi 10 1021 ja00068a079 Hargaden Grainne C Guiry Patrick J 2007 11 05 The Development of the Asymmetric Nozaki Hiyama Kishi Reaction Advanced Synthesis amp Catalysis 349 16 2407 2424 doi 10 1002 adsc 200700324 Kim In Su Ngai Ming Yu Krische Michael J 2008 11 05 Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level via Transfer Hydrogenative Coupling of Allyl Acetate Departure from Chirally Modified Allyl Metal Reagents in Carbonyl Addition Journal of the American Chemical Society 130 44 14891 14899 doi 10 1021 ja805722e ISSN 0002 7863 PMC 2890235 PMID 18841896 Brittain Dominic E A Griffiths Jones Charlotte M Linder Michael R Smith Martin D McCusker Catherine Barlow Jaqueline S Akiyama Ryo Yasuda Kosuke Ley Steven V 2005 Total Synthesis of Antascomicin B Angewandte Chemie International Edition 44 18 2732 2737 doi 10 1002 anie 200500174 ISSN 1521 3773 PMID 15806607 Wang Gang Krische Michael J 2016 07 06 Total Synthesis of SCH 351448 Efficiency via Chemoselectivity and Redox Economy Powered by Metal Catalysis Journal of the American Chemical Society 138 26 8088 8091 doi 10 1021 jacs 6b04917 ISSN 0002 7863 PMC 4935581 PMID 27337561 Retrieved from https en wikipedia org w index php title Carbonyl allylation amp oldid 1172815217, wikipedia, wiki, book, books, library,
