196:
In the
Roskamp reaction, the alpha position of the formed β-ketoester can potentially be a chiral center, so asymmetric variants of the Roskamp reaction were investigated. In 2009, Maruoka and co-workers reported a Lewis acid-catalyzed asymmetric Roskamp reaction. The chiral information is introduced
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Li, Wei; Wang, Jun; Hu, Xiaolei; Shen, Ke; Wang, Wentao; Chu, Yangyang; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming (2010-06-30). "Catalytic
Asymmetric Roskamp Reaction of α-Alkyl-α-diazoesters with Aromatic Aldehydes: Highly Enantioselective Synthesis of α-Alkyl-β-keto Esters".
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A disadvantage of the
Roskamp–Feng reaction is that the substrate is limited to aromatic aldehydes. The authors also demonstrated that the ketoester products can be further reduced to access chiral 1,3-diols, a useful class of building blocks in natural product synthesis.
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Holmquist, Christopher R.; Roskamp, Eric J. (1990). "The conversion of olefins to β-keto esters: Ozonolysis of olefins followed by in situ reduction with tin(II) chloride in the presence of ethyl diazoacetate. Author links open overlay panel".
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Hashimoto, Takuya; Miyamoto, Hisashi; Naganawa, Yuki; Maruoka, Keiji (2009-08-19). "Stereoselective
Synthesis of α-Alkyl-β-keto Imides via Asymmetric Redox C−C Bond Formation between α-Alkyl-α-diazocarbonyl Compounds and Aldehydes".
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Compared to the
Roskamp–Feng reaction, this method has a broader scope of aldehydes, notably being compatible with aliphatic aldehydes. In 2015, the same group reported asymmetric Roskamp reaction of the α-aryl diazo
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Bandyopadhyay, Anupam; Agrawal, Neha; Mali, Sachitanand M.; Jadhav, Sandip V.; Gopi, Hosahudya N. (2010). "Tin(ii) chloride assisted synthesis of N-protected γ-amino β-keto esters through semipinacol rearrangement".
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Shin, Sung Ho; Baek, Eun Hee; Hwang, Geum-Sook; Ryu, Do Hyun (2015-10-02). "Enantioselective
Synthesis of syn-α-Aryl-β-hydroxy Weinreb Amides: Catalytic Asymmetric Roskamp Reaction of α-Aryl Diazo Weinreb Amides".
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Diazo compounds are ambiphilic reagents. According to its resonance structure, the carbon adjacent to the diazo group has partial negative charge. If R’ = H, this can be regarded as a hydride-transfer process.
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Gao, Lizhu; Kang, Byung Chul; Hwang, Geum-Sook; Ryu, Do Hyun (2012-08-13). "Enantioselective
Synthesis of α-Alkyl-β-ketoesters: Asymmetric Roskamp Reaction Catalyzed by an Oxazaborolidinium Ion".
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Holmquist, Christopher R.; Roskamp, Eric J. (1989-07-01). "A selective method for the direct conversion of aldehydes into β-keto esters with ethyl diazoacetate catalyzed by tin(II) chloride".
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Padwa, Albert; Hornbuckle, Susan F.; Zhang, Zhijia; Zhi, Lin (1990). "Synthesis of 1,3-diketones using α-diazo ketones and aldehydes in the presence of tin(II) chloride".
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126:; however, β-ketoesters were the only products to be observed. The authors also noted that aliphatic aldehyde gave higher yield than aromatic aldehydes due to
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Holmquist, Christopher R. (1992-02-25). "Tin(II) chloride catalyzed addition of diazo sulfones, diazo phosphine oxides, and diazo phosphonates to aldehydes".
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The
Roskamp reaction was published seminally in 1989 by Roskamp and co-workers. The authors initially proposed that the reaction would convert aldehydes to
183:, where tin(II) chloride would serve as both the reducing agent in the ozonolysis step as well as the Lewis acid catalyst in the Roskamp reaction step.
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Xiaohua, Liu; Lili, Lin; Xiaoming, Feng (2014). "Chiral N,N′-dioxide ligands: synthesis, coordination chemistry and asymmetric catalysis".
130:. Additionally, the mild reaction conditions shows advantages in preventing side reactions and increasing functional group tolerance.
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Guttenberger, Nikolaus; Breinbauer, Rolf (2017). "C-H and C-C bond insertion reactions of diazo compounds into aldehydes".
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Zhang, Yan; Wang, Jianbo (2009-09-02). "Recent development of reactions with α-diazocarbonyl compounds as nucleophiles".
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In 2010, the Feng group developed a chiral Sc-catalyzed enantioselective
Roskamp reaction, sometimes referred to as the
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The
Roskamp reaction was utilized in the total synthesis of (+)-Galbulimima Alkaloid 13 and (+)-Himgaline.
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Lewis acid catalysts, which are generated from the corresponding oxazaborolidines by protonation with
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developed a catalytic, asymmetric Roskamp reaction with broad applicability. They utilized
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as catalysts. The reaction is notable for its mild reaction conditions and selectivity.
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Aldehydes containing protected amines are tolerated under Roskamp conditions.
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In 1992, Roskamp and co-workers expanded the scope of diazoacetate to diazo
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describing the reaction between α-diazoesters (such as
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220:chiral ligands were used, an emerging class of
197:by chiral auxiliaries from the diazo compound.
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755:Journal of the American Chemical Society
594:Journal of the American Chemical Society
550:Journal of the American Chemical Society
664:Angewandte Chemie International Edition
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304:Büchner–Curtius–Schlotterbeck reaction
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492:Organic & Biomolecular Chemistry
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368:The Journal of Organic Chemistry
331:The Journal of Organic Chemistry
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534:10.1016/S0040-4039(00)97786-4
437:10.1016/S0040-4039(00)91877-X
720:10.1021/acs.orglett.5b02268
637:Organic Chemistry Frontiers
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251:In 2012, Do Hyun Ryu from
247:Other Asymmetric reactions
410:10.1016/j.tet.2017.10.051
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270:Oxazaborolidine catalyst
452:Chemical Communications
253:Sungkyunkwan University
676:10.1002/anie.201204350
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257:oxazaborolidinium ion
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214:Roskamp–Feng reaction
208:Roskamp–Feng reaction
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124:Wittig type reaction
556:(32): 11280–11281.
521:Tetrahedron Letters
425:Tetrahedron Letters
381:10.1021/jo00305a029
344:10.1021/jo00275a006
187:Asymmetric Variants
801:Chemical reactions
796:Coupling reactions
649:10.1039/C3QO00059A
504:10.1039/C0OB00199F
309:Meerwein arylation
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75:ethyl diazoacetate
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714:(19): 4746–4749.
670:(33): 8322–8325.
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600:(25): 8532–8533.
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528:(35): 4991–4994.
498:(21): 4855–4860.
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404:(49): 6815–6829.
375:(18): 5297–5299.
338:(14): 3258–3260.
222:privileged ligand
63:organic chemistry
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50:Coupling reaction
33:Roskamp reaction
27:Chemical reaction
16:(Redirected from
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38:Named after
397:Tetrahedron
231:Feng ligand
128:enolization
79:Lewis acids
790:Categories
315:References
181:ozonolysis
114:Background
728:1523-7060
684:1521-3773
614:0002-7863
570:0002-7863
468:1364-548X
352:0022-3263
155:Mechanism
81:(such as
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736:26393875
692:22821683
622:20527752
578:19630397
476:19724784
298:See also
142:sulfones
177:Olefins
120:alkenes
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95:, and
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69:is a
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732:PMID
724:ISSN
688:PMID
680:ISSN
618:PMID
610:ISSN
574:PMID
566:ISSN
472:PMID
464:ISSN
348:ISSN
97:GeCl
90:SnCl
764:doi
760:129
716:doi
672:doi
645:doi
602:doi
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61:In
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