An Iron/Amine-Catalyzed Cascade Process for the Enantioselective Functionalization of Allylic Alcohols

Three is a lucky number: An enantioselective transformation of allylic alcohols into β‐chiral saturated alcohols has been developed by combining two distinct metal‐ and organocatalyzed catalytic cycles. This waste‐free triple cascade process merges an iron‐catalyzed borrowing‐hydrogen step with an a...

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Published inAngewandte Chemie International Edition Vol. 52; no. 49; pp. 12883 - 12887
Main Authors Quintard, Adrien, Constantieux, Thierry, Rodriguez, Jean
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 02.12.2013
WILEY‐VCH Verlag
Wiley
Wiley Subscription Services, Inc
Wiley-VCH Verlag
EditionInternational ed. in English
Subjects
Online AccessGet full text
ISSN1433-7851
1521-3773
1521-3773
DOI10.1002/anie.201307295

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Abstract Three is a lucky number: An enantioselective transformation of allylic alcohols into β‐chiral saturated alcohols has been developed by combining two distinct metal‐ and organocatalyzed catalytic cycles. This waste‐free triple cascade process merges an iron‐catalyzed borrowing‐hydrogen step with an aminocatalyzed nucleophilic addition reaction.
AbstractList Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction.Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction.
An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition
Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction.
Three is a lucky number: An enantioselective transformation of allylic alcohols into [beta]-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction.
Author Quintard, Adrien
Rodriguez, Jean
Constantieux, Thierry
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  givenname: Thierry
  surname: Constantieux
  fullname: Constantieux, Thierry
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  givenname: Jean
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  fullname: Rodriguez, Jean
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Copyright Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
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Issue 49
Keywords ORGANIC-SYNTHESIS
C BOND FORMATION
BORROWING HYDROGEN
METAL-DIENE COMPLEXES
ALPHA,BETA-UNSATURATED ALDEHYDES
asymmetric catalysis
dual catalysis
hydrogen transfer
MEDIATED 2+2+1 CYCLOADDITIONS
OPPENAUER-TYPE OXIDATION
IRON-CATALYST
organocatalysis
CARBON-MONOXIDE
TRANSITION-METAL
iron
Language English
License http://onlinelibrary.wiley.com/termsAndConditions#vor
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Distributed under a Creative Commons Attribution 4.0 International License: http://creativecommons.org/licenses/by/4.0
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Notes ArticleID:ANIE201307295
Financial support from the Centre National de la Recherche Scientifique (CNRS) and Aix-Marseille Université is gratefully acknowledged. The authors gratefully thank Marion Jean and Nicolas Vanthuyne (Aix-Marseille Université) for chiral-phase HPLC analysis of all compounds.
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Aix-Marseille Université
Centre National de la Recherche Scientifique (CNRS)
istex:D01222CFC128AC105801B1264083AC76D119DFA2
Financial support from the Centre National de la Recherche Scientifique (CNRS) and Aix‐Marseille Université is gratefully acknowledged. The authors gratefully thank Marion Jean and Nicolas Vanthuyne (Aix‐Marseille Université) for chiral‐phase HPLC analysis of all compounds.
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PublicationTitle Angewandte Chemie International Edition
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References A. Bartoszewicz, R. Marcos, S. Sahoo, A. K. Inge, X. Zou, N. Martin-Matute, Chem. Eur. J. 2012, 18, 14510-14519
A. L. E. Larsson, B. A. Persson, J. E. Bäckvall, Angew. Chem. 1997, 109, 1256-1258
A. Pagnoux-Ozherelyeva, N. Pannetier, M. D. Mbaye, S. Gaillard, J.-L. Renaud, Angew. Chem. 2012, 124, 5060-5064
M. Rueping, H. Sundén, L. Hubener, E. Sugiono, Chem. Commun. 2012, 48, 2201-2203
A. Carlone, M. Marigo, C. North, A. Nada, K. A. Jørgensen, Chem. Commun. 2006, 4928-4930
S. Bertelsen, K. A. Jørgensen, Chem. Soc. Rev. 2009, 38, 2178-2189
C. A. Busacca, D. R. Fandrick, J. J. Song, C. H. Senanayake, Adv. Synth. Catal. 2011, 353, 1825-1864.
T. C. Johnson, G. J. Clarkson, M. Wills, Organometallics 2011, 30, 1859-1868
C. P. Casey, H. Guan, J. Am. Chem. Soc. 2007, 129, 5816-5817
S. A. Moyer, T. Funk, Tetrahedron Lett. 2010, 51, 5430-5433
J. Yang, X. Liu, D.-L. Meng, H.-Y. Chen, Z.-H. Zong, T.-T. Feng, K. Sun, Adv. Synth. Catal. 2012, 354, 328-334; for an early example of dual iron-/ organocatalysis, see
Angew. Chem. Int. Ed. 2008, 47, 6138-6171.
H.-J. Knölker, E. Baum, H. Goesmann, R. Klauss, Angew. Chem. 1999, 111, 2196-2199
Angew. Chem. Int. Ed. 2001, 40, 4475.
J.-Q. Li, P. G. Andersson, Chem. Commun. 2013, 49, 6131-6133.
K. A. Ahrendt, C. J. Borths, D. W. C. MacMillan, J. Am. Chem. Soc. 2000, 122, 4243-4244
P. A. Slatford, M. K. Whittlesey, J. M. J. Williams, Tetrahedron Lett. 2006, 47, 6787-6789
M. Marigo, T. C. Wabnitz, D. Fielenbach, K. A. Jørgensen, Angew. Chem. 2005, 117, 804-807
C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025
G. E. Dobereiner, R. H. Crabtree, Chem. Rev. 2010, 110, 681-703
T. N. Plank, J. L. Drake, D. K. Kim, T. W. Funk, Adv. Synth. Catal. 2012, 354, 597-601.
Angew. Chem. Int. Ed. 2011, 50, 2354-2358
M. K. Thorson, K. L. Klinkel, J. Wang, T. J. Williams, Eur. J. Inorg. Chem. 2009, 295-302
A. J. A. Watson, J. M. J. Williams, Science 2010, 329, 635-636
C. Gunanathan, D. Milstein, Science 2013, 341, 1229712.
S. Zhou, S. Fleischer, K. Junge, M. Beller, Angew. Chem. 2011, 123, 5226-5230
Angew. Chem. Int. Ed. 2008, 47, 121-125
S. Cabrera, J. Aleman, P. Bolze, S. Bertelsen, K. A. Jørgensen, Angew. Chem. 2008, 120, 127-131
Angew. Chem. Int. Ed. 2005, 44, 4212-4215.
Angew. Chem. Int. Ed. 1999, 38, 2064-2066
S. Brandau, A. Landa, J. Franzen, M. Marigo, K. A. Jørgensen, Angew. Chem. 2006, 118, 4411-4415
M. G. Coleman, A. N. Brown, B. A. Bolton, H. Guan, Adv. Synth. Catal. 2010, 352, 967-970
J. Moran, M. J. Krische, Pure Appl. Chem. 2012, 84, 1729-1739, and references therein
P. Melchiorre, M. Marigo, A. Carlone, G. Bartoli, Angew. Chem. 2008, 120, 6232-6265
A. Quintard, A. Alexakis, C. Mazet, Angew. Chem. 2011, 123, 2402-2406
S. Chercheja, P. Eilbracht, Adv. Synth. Catal. 2007, 349, 1897-1905
D. J. Shermer, P. A. Slatford, D. D. Edney, J. M. J. Williams, Tetrahedron: Asymmetry 2007, 18, 2845-2848.
A. Tlili, J. Schranck, H. Neumann, M. Beller, Chem. Eur. J. 2012, 18, 15935-15939
S. Bähn, S. Imm, L. Neubert, M. Zhang, H. Neumann, M. Beller, ChemCatChem 2011, 3, 1853-1864
Angew. Chem. Int. Ed. 2005, 44, 794-797
H.-J. Knölker, J. Heber, Synlett 1993, 924-926
Angew. Chem. Int. Ed. 2012, 51, 4976-4980
H.-J. Knölker, J. Heber, C. H. Mahler, Synlett 1992, 1002-1004
Angew. Chem. Int. Ed. 2013, 52, 5120-5124
C. P. Casey, H. Guan, J. Am. Chem. Soc. 2009, 131, 2499-2507
S. Gaillard, J.-L. Renaud, ChemSusChem 2008, 1, 505-509
Z. Du, Z. Shao, Chem. Soc. Rev. 2013, 42, 1337-1378.
M. P. Sibi, M. Hasegawa, J. Am. Chem. Soc. 2007, 129, 4124-4125.
X. Lu, Y. Zhang, P. Yun, M. Zhang, T. Li, Org. Biomol. Chem. 2013, 11, 5264-5277.
Angew. Chem. Int. Ed. 2011, 50, 5120-5124
A. E. Allen, D. W. C. MacMillan, Chem. Sci. 2012, 3, 633-658
Y. Hayashi, H. Gotoh, T. Hayashi, M. Shoji, Angew. Chem. 2005, 117, 4284-4287
P. J. Black, W. Harris, J. M. J. Williams, Angew. Chem. 2001, 113, 4607
M. Rueping, H. Sundén, E. Sugiono, Chem. Eur. J. 2012, 18, 3649-3653
M. Rueping, J. Dufour, M. S. Maji, Chem. Commun. 2012, 48, 3406-3408.
M. G. Edwards, R. F. R. Jazzar, B. M. Paine, D. J. Shermer, M. K. Whittlesey, J. M. J. Williams, D. D. Edney, Chem. Commun. 2004, 90-91
Angew. Chem. Int. Ed. 2006, 45, 4305-4309.
S. P. Lathrop, T. Rovis, J. Am. Chem. Soc. 2009, 131, 13628-13630.
P. Hermange, F. Portalier, C. Thomassigny, C. Greck, Tetrahedron Lett. 2013, 54, 1052-1055
Angew. Chem. Int. Ed. Engl. 1997, 36, 1211-1212
O. Abillard, B. Breit, Adv. Synth. Catal. 2007, 349, 1891-1895
G. Guillena, D. J. Ramon, M. Yus, Chem. Rev. 2010, 110, 1611-1641
S. Fleischer, S. S. Zhou, K. Junge, M. Beller, Angew. Chem. 2013, 125, 5224-5228
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Larsson, A. L. E. (000327410300018.35) 1997; 109
Busacca, CA (WOS:000294179400001) 2011; 353
Li, JQ (WOS:000320332500005) 2013; 49
Edwards, MG (WOS:000188239000039) 2004
Fleischer, S. (000327410300018.23) 2013; 125
Guillena, G (WOS:000275586900012) 2010; 110
Sibi, MP (WOS:000245723800008) 2007; 129
Zhong, C (WOS:000278888700001) 2010; 2010
Yang, J (WOS:000300448400009) 2012; 354
Du, ZT (WOS:000313596300019) 2013; 42
Black, PJ (WOS:000172626600035) 2001; 40
Quintard, A (WOS:000288036300029) 2011; 50
Ahrendt, KA (WOS:000086950500045) 2000; 122
Bähn, S (WOS:000297791400003) 2011; 3
Zhou, SL (WOS:000290665100016) 2011; 50
Cabrera, S (WOS:000251911400021) 2008; 47
Casey, CP (WOS:000263576100035) 2009; 131
Thorson, MK (WOS:000262897500013) 2009
Carlone, A (WOS:000242382400014) 2006
Fleischer, S (WOS:000318799800022) 2013; 52
Quintard, A. (000327410300018.49) 2011; 123
Gunanathan, C (WOS:000321959300033) 2013; 341
Pagnoux-Ozherelyeva, A. (000327410300018.47) 2012; 124
Melchiorre, P. (000327410300018.43) 2008; 120
Slatford, PA (WOS:000240670800018) 2006; 47
Johnson, TC (WOS:000289008700015) 2011; 30
Allen, AE (WOS:000299949500001) 2012; 3
Hayashi, Y (WOS:000230354100016) 2005; 44
Hermange, P (WOS:000315063700003) 2013; 54
Lathrop, SP (WOS:000270186600029) 2009; 131
Knolker, H.-J. (000327410300018.31) 1999; 111
Bartoszewicz, A (WOS:000310474800036) 2012; 18
Bertelsen, S (WOS:000268184600003) 2009; 38
Shermer, DJ (WOS:000253095800001) 2007; 18
Melchiorre, P (WOS:000258355200004) 2008; 47
Tlili, A (WOS:000312163500006) 2012; 18
Marigo, M (WOS:000226711700024) 2005; 44
Watson, AJA (WOS:000280602700023) 2010; 329
KNOLKER, HJ (WOS:A1992KG62000021) 1992
Black, P. J. (000327410300018.8) 2001; 113
Chercheja, S (WOS:000249313100012) 2007; 349
Marigo, M. (000327410300018.41) 2005; 117
Abillard, O (WOS:000249313100011) 2007; 349
Brandau, S (WOS:000238746100014) 2006; 45
Moyer, SA (WOS:000282381000020) 2010; 51
Plank, TN (WOS:000301172600009) 2012; 354
Rueping, M (WOS:000301444900025) 2012; 18
Hayashi, Y. (000327410300018.28) 2005; 117
Gaillard, S (WOS:000265912100002) 2008; 1
Rueping, M (WOS:000301193100011) 2012; 48
Casey, CP (WOS:000246180200016) 2007; 129
Zhou, S. (000327410300018.63) 2011; 123
Larsson, ALE (WOS:A1997XJ96000021) 1997; 36
Dobereiner, GE (WOS:000274705900005) 2010; 110
Knölker, HJ (WOS:000081511900060) 1999; 38
KNOLKER, HJ (WOS:A1993MM35700016) 1993
Pagnoux-Ozherelyeva, A (WOS:000303925200040) 2012; 51
Rueping, M (WOS:000300533500009) 2012; 48
Cabrera, S. (000327410300018.12) 2008; 120
Brandau, S. (000327410300018.10) 2006; 118
Coleman, MG (WOS:000277298800005) 2010; 352
Lu, X (WOS:000322944900009) 2013; 11
Moran, J (WOS:000306643000006) 2012; 84
References_xml – reference: H.-J. Knölker, J. Heber, Synlett 1993, 924-926;
– reference: A. Bartoszewicz, R. Marcos, S. Sahoo, A. K. Inge, X. Zou, N. Martin-Matute, Chem. Eur. J. 2012, 18, 14510-14519;
– reference: P. Melchiorre, M. Marigo, A. Carlone, G. Bartoli, Angew. Chem. 2008, 120, 6232-6265;
– reference: P. Hermange, F. Portalier, C. Thomassigny, C. Greck, Tetrahedron Lett. 2013, 54, 1052-1055;
– reference: Angew. Chem. Int. Ed. 2013, 52, 5120-5124;
– reference: A. L. E. Larsson, B. A. Persson, J. E. Bäckvall, Angew. Chem. 1997, 109, 1256-1258;
– reference: G. E. Dobereiner, R. H. Crabtree, Chem. Rev. 2010, 110, 681-703;
– reference: Angew. Chem. Int. Ed. 2006, 45, 4305-4309.
– reference: S. Fleischer, S. S. Zhou, K. Junge, M. Beller, Angew. Chem. 2013, 125, 5224-5228;
– reference: S. Gaillard, J.-L. Renaud, ChemSusChem 2008, 1, 505-509;
– reference: J. Moran, M. J. Krische, Pure Appl. Chem. 2012, 84, 1729-1739, and references therein;
– reference: Z. Du, Z. Shao, Chem. Soc. Rev. 2013, 42, 1337-1378.
– reference: X. Lu, Y. Zhang, P. Yun, M. Zhang, T. Li, Org. Biomol. Chem. 2013, 11, 5264-5277.
– reference: A. J. A. Watson, J. M. J. Williams, Science 2010, 329, 635-636;
– reference: M. G. Coleman, A. N. Brown, B. A. Bolton, H. Guan, Adv. Synth. Catal. 2010, 352, 967-970;
– reference: M. Rueping, J. Dufour, M. S. Maji, Chem. Commun. 2012, 48, 3406-3408.
– reference: H.-J. Knölker, E. Baum, H. Goesmann, R. Klauss, Angew. Chem. 1999, 111, 2196-2199;
– reference: Angew. Chem. Int. Ed. 2012, 51, 4976-4980;
– reference: S. Zhou, S. Fleischer, K. Junge, M. Beller, Angew. Chem. 2011, 123, 5226-5230;
– reference: Angew. Chem. Int. Ed. 2005, 44, 794-797;
– reference: Angew. Chem. Int. Ed. 2008, 47, 121-125;
– reference: P. A. Slatford, M. K. Whittlesey, J. M. J. Williams, Tetrahedron Lett. 2006, 47, 6787-6789;
– reference: S. Cabrera, J. Aleman, P. Bolze, S. Bertelsen, K. A. Jørgensen, Angew. Chem. 2008, 120, 127-131;
– reference: C. A. Busacca, D. R. Fandrick, J. J. Song, C. H. Senanayake, Adv. Synth. Catal. 2011, 353, 1825-1864.
– reference: K. A. Ahrendt, C. J. Borths, D. W. C. MacMillan, J. Am. Chem. Soc. 2000, 122, 4243-4244;
– reference: S. Chercheja, P. Eilbracht, Adv. Synth. Catal. 2007, 349, 1897-1905;
– reference: M. Marigo, T. C. Wabnitz, D. Fielenbach, K. A. Jørgensen, Angew. Chem. 2005, 117, 804-807;
– reference: O. Abillard, B. Breit, Adv. Synth. Catal. 2007, 349, 1891-1895;
– reference: M. K. Thorson, K. L. Klinkel, J. Wang, T. J. Williams, Eur. J. Inorg. Chem. 2009, 295-302;
– reference: T. C. Johnson, G. J. Clarkson, M. Wills, Organometallics 2011, 30, 1859-1868;
– reference: Angew. Chem. Int. Ed. 2008, 47, 6138-6171.
– reference: Angew. Chem. Int. Ed. Engl. 1997, 36, 1211-1212;
– reference: S. A. Moyer, T. Funk, Tetrahedron Lett. 2010, 51, 5430-5433;
– reference: Y. Hayashi, H. Gotoh, T. Hayashi, M. Shoji, Angew. Chem. 2005, 117, 4284-4287;
– reference: S. Brandau, A. Landa, J. Franzen, M. Marigo, K. A. Jørgensen, Angew. Chem. 2006, 118, 4411-4415;
– reference: S. Bähn, S. Imm, L. Neubert, M. Zhang, H. Neumann, M. Beller, ChemCatChem 2011, 3, 1853-1864;
– reference: Angew. Chem. Int. Ed. 2001, 40, 4475.
– reference: Angew. Chem. Int. Ed. 2011, 50, 5120-5124;
– reference: T. N. Plank, J. L. Drake, D. K. Kim, T. W. Funk, Adv. Synth. Catal. 2012, 354, 597-601.
– reference: A. E. Allen, D. W. C. MacMillan, Chem. Sci. 2012, 3, 633-658;
– reference: C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025;
– reference: Angew. Chem. Int. Ed. 1999, 38, 2064-2066;
– reference: H.-J. Knölker, J. Heber, C. H. Mahler, Synlett 1992, 1002-1004;
– reference: G. Guillena, D. J. Ramon, M. Yus, Chem. Rev. 2010, 110, 1611-1641;
– reference: S. Bertelsen, K. A. Jørgensen, Chem. Soc. Rev. 2009, 38, 2178-2189;
– reference: M. G. Edwards, R. F. R. Jazzar, B. M. Paine, D. J. Shermer, M. K. Whittlesey, J. M. J. Williams, D. D. Edney, Chem. Commun. 2004, 90-91;
– reference: Angew. Chem. Int. Ed. 2005, 44, 4212-4215.
– reference: M. P. Sibi, M. Hasegawa, J. Am. Chem. Soc. 2007, 129, 4124-4125.
– reference: C. Gunanathan, D. Milstein, Science 2013, 341, 1229712.
– reference: M. Rueping, H. Sundén, E. Sugiono, Chem. Eur. J. 2012, 18, 3649-3653;
– reference: D. J. Shermer, P. A. Slatford, D. D. Edney, J. M. J. Williams, Tetrahedron: Asymmetry 2007, 18, 2845-2848.
– reference: C. P. Casey, H. Guan, J. Am. Chem. Soc. 2007, 129, 5816-5817;
– reference: A. Pagnoux-Ozherelyeva, N. Pannetier, M. D. Mbaye, S. Gaillard, J.-L. Renaud, Angew. Chem. 2012, 124, 5060-5064;
– reference: Angew. Chem. Int. Ed. 2011, 50, 2354-2358;
– reference: J.-Q. Li, P. G. Andersson, Chem. Commun. 2013, 49, 6131-6133.
– reference: M. Rueping, H. Sundén, L. Hubener, E. Sugiono, Chem. Commun. 2012, 48, 2201-2203;
– reference: A. Quintard, A. Alexakis, C. Mazet, Angew. Chem. 2011, 123, 2402-2406;
– reference: P. J. Black, W. Harris, J. M. J. Williams, Angew. Chem. 2001, 113, 4607;
– reference: A. Tlili, J. Schranck, H. Neumann, M. Beller, Chem. Eur. J. 2012, 18, 15935-15939;
– reference: S. P. Lathrop, T. Rovis, J. Am. Chem. Soc. 2009, 131, 13628-13630.
– reference: A. Carlone, M. Marigo, C. North, A. Nada, K. A. Jørgensen, Chem. Commun. 2006, 4928-4930;
– reference: J. Yang, X. Liu, D.-L. Meng, H.-Y. Chen, Z.-H. Zong, T.-T. Feng, K. Sun, Adv. Synth. Catal. 2012, 354, 328-334; for an early example of dual iron-/ organocatalysis, see:
– reference: C. P. Casey, H. Guan, J. Am. Chem. Soc. 2009, 131, 2499-2507;
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Snippet Three is a lucky number: An enantioselective transformation of allylic alcohols into β‐chiral saturated alcohols has been developed by combining two distinct...
Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct...
Three is a lucky number: An enantioselective transformation of allylic alcohols into [beta]-chiral saturated alcohols has been developed by combining two...
An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed...
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SubjectTerms asymmetric catalysis
Chemical Sciences
Chemistry
Chemistry, Multidisciplinary
dual catalysis
hydrogen transfer
iron
Organic chemistry
organocatalysis
Physical Sciences
Science & Technology
Title An Iron/Amine-Catalyzed Cascade Process for the Enantioselective Functionalization of Allylic Alcohols
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