OMe O M. Watson, JACS (2011) 17142 A. Baba , Chem. Com. (2013) 11620 - - PowerPoint PPT Presentation

V.А. Shcherbinin, V.V. Konshin

Kuban State University

Lewis acid-mediated mono- and bis-addition of C- nucleophiles to 1,3-dioxolan-4-ones.

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• A. Romero, JACS (2000) 168

O OMe

• A. Baba, Chem. Com. (2013) 11620
• M. Watson, JACS (2011) 17142

O OMe

• H. Huang, ChemCat. (2015) 250

O OAc Br

O+

Fe(OTs)3 TMSOTf BF3*OEt2

• M. Watson, OL (2015) 3857

O OAc n

• S. Lee, JACS (2017) 2156

O OAc R

TMSOTf or imido- diphosphorimidate

• M. Beaver, Angew. (2016) 1816

BF3*OEt2

O OAc

BF3*OEt2

R

• S. Murata, TL (1982) 2601

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Nucleophilic addition to an oxocarbenium cation generated from 1,3-dioxolan-4-ones

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Reaction of 1,3-dioxolan-4-ones with silicon containing nucleophiles

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Nucleophile Product Yield, % Nucleophile Product Yield, % 1 84 (62:38) 5 55 (61:39) 2 76 (76:24) 6 63 (64:36) 3 62 (61:39) 7

• 4

82 (57:43) 8

• Ph-C≡C-SiMe3

Ph-C≡C-H

Reaction of 1,3-dioxolan-4-ones with 1-alkynes

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Nucleophile Product Yield, % Nucleophile Product Yield, % 1 75 (60:40) 5 50 (75:25) 2 73 (80:20) 6 53 (75:25) 3 67 (75:25) 7 45 (82:18) 4 45 (80:20) 8 33 (83:17)

Mechanism of formation of diastereomeric pair

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Reaction of 1,3-dioxolan-4-ones with aromatic compounds

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R Nucleophile Product Yield, % R Nucleophile Product Yield, % Ph 54 Ph 76 Ph 28 p-NO2Ph 15 Ph trace Ph

Competitive addition of nucleophiles to 1,3-dioxolan-4-one

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Comparison of the nucleophilicity of the reagents involved in competitive addition

• Prof. H. Mayr, http:/ / www.cup.lmu.de/oc/ mayr/ DBintro.html

Proposed mechanistic scheme for the transformations

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T etrahedron Letters, 2018, 3005-3309

This work was financially supported by the Russian Science Foundation (project No. 17-73-10251)

Conclusion

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