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Radical-Induced 1, 2-Migrations of Boron Ate Complexes
Speaker： Shutao Qi
Supervisor: Prof. Junliang Zhang
1
1. Introduction
2. Radical-Induced 1, 2-Migrations of Boron Ate Complexes
2.1 Radical-Induced 1, 2-Boron Ate Migration to sp2 Carbons
2.2 Radical-Induced 1, 2-Boron Ate Migration to sp3 Carbons
3. Summary and Outlook
2
Content
1. Introduction
2. Radical-Induced 1,2-Migrations of Boron Ate Complexes
2.1 Radical-Induced 1,2-Boron Ate Migration to sp2 Carbons
2.2 Radical-Induced 1,2-Boron Ate Migration to sp3 Carbons
3. Summary and Outlook
3
Content
4
M. S. Kharasch et al, J. Am. Chem. Soc., 1944, 66, 1438.
H. Wieland et al, Chem. Ber., 1911, 44, 2550.
J. Y. Do et al, Chem. Commun., 1995, 1607.
Y.-Q. Tu et al, Chem. Soc. Rev. 2015, 44, 5220
Radical-induced 1,2-migrations
Introduction
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M. E. D. Hillman, J. Am. Chem. Soc. 1962, 84, 4715.
D. S. Matteson et al, J. Am. Chem. Soc. 1963, 85, 2599.
D. S. Matteson, R. Ray, J. Am. Chem. Soc. 1980, 102, 7590
G. Zweifel et al, J. Am. Chem. Soc. 1967, 89, 3652
1,2-Metalate migrations of boron ate complexes
Introduction
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Introduction
Radical-induced 1,2-migrations of boron ate complexes
Content
1. Introduction
2. Radical-Induced 1, 2-Migrations of Boron Ate Complexes
2.1 Radical-Induced 1, 2-Boron Ate Migration to sp2 Carbons
2.2 Radical-Induced 1, 2-Boron Ate Migration to sp3 Carbons
3. Summary and Outlook
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A. Studer et al, Science, 2017, 355, 936
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1, 2-Migration to sp2 Carbons
Selected examples
First example
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Mechanistic study
1, 2-Migration to sp2 Carbons
A. Studer et al, Science, 2017, 355, 936
V. K. Aggarwal et al, J. Am. Chem. Soc. 2017, 139, 5736
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1, 2-Migration to sp2 Carbons
Selected examples
Light initiation
Proposed mechanism
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1, 2-Migration to sp2 Carbons
V. K. Aggarwal et al, J. Am. Chem. Soc. 2017, 139, 5736
P. Renaud et al, Chem. Eur. J. 2018, 24, 11498
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Mechanistic study
1, 2-Migration to sp2 Carbons
Proposed mechanism
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1, 2-Migration to sp2 Carbons
Radical clock experiment
Atom transfer experiment
P. Renaud et al, Chem. Eur. J. 2018, 24, 11498
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1, 2-Migration to sp2 Carbons
Radical 1,2-migration experiment
Oxygen 1,2-migration experiment
P. Renaud et al, Chem. Eur. J. 2018, 24, 11498
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1, 2-Migration to sp2 Carbons
J. P. Morken et al, J. Am. Chem. Soc. 2017, 139, 17293
Metal-induced 1,2-migration
For non-active alkyl halide
For active alkyl halide
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1, 2-Migration to sp2 Carbons
Proposed mechanism
J. P. Morken et al, J. Am. Chem. Soc. 2017, 139, 17293
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1, 2-Migration to sp2 Carbons
Control experiment
J. P. Morken et al, J. Am. Chem. Soc. 2017, 139, 17293
(a)
(b)
(c)
(d)
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1, 2-Migration to sp2 Carbons
Proposed mechanism
J. P. Morken et al, J. Am. Chem. Soc. 2017, 139, 17293
Z. Shi et al, Angew. Chem. Int. Ed. 2019, 58, 9448
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1, 2-Migration to sp2 Carbons
Boron migration
Selected examples
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1, 2-Migration to sp2 Carbons
Proposed mechanism
Z. Shi et al, Angew. Chem. Int. Ed. 2019, 58, 9448
21A. Studer et al, Org. Lett. 2018, 20, 3666
1, 2-Migration to sp2 Carbons
Proposed mechanism
1,4-Diene ate complexes
Selected examples
22V. K. Aggarwal et al, Angew. Chem. Int. Ed. 2017, 56, 1810.
1, 2-Migration to sp2 Carbons
Heterocycle ate complexes
Selected examples
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Proposed mechanism
1, 2-Migration to sp2 Carbons
V. K. Aggarwal et al, Angew. Chem. Int. Ed. 2017, 56, 1810.
24A. Studer et al, Angew. Chem. Int. Ed. 2020, 59, 15468
1, 2-Migration to sp2 Carbons
Aryl-aryl coupling
Selected examples
25
Proposed mechanism
1, 2-Migration to sp2 Carbons
A. Studer et al, Angew. Chem. Int. Ed. 2020, 59, 15468
Content
1. Introduction
2. Radical-Induced 1, 2-Migrations of Boron Ate Complexes
2.1 Radical-Induced 1, 2-Boron Ate Migration to sp2 Carbons
2.2 Radical-Induced 1, 2-Boron Ate Migration to sp3 Carbons
3. Summary and Outlook
26
27V. K. Aggarwal et al, J. Am. Chem. Soc. 2019, 141, 9511
1, 2-Migration to sp3 Carbons
Select examples
BCB boron ate complexes
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Proposed mechanism
1, 2-Migration to sp3 Carbons
V. K. Aggarwal et al, J. Am. Chem. Soc. 2019, 141, 9511
29A. Studer et al, J. Am. Chem. Soc. 2019, 141, 14126
1, 2-Migration to sp3 Carbons
HAT induced 1,2-migration
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Proposed mechanism
1, 2-Migration to sp3 Carbons
Stern-Volmer fluorescence quenching experiments
A. Studer et al, J. Am. Chem. Soc. 2019, 141, 14126
Boron ate
complex
CF3I
Fac-Ir(ppy)3 Solutions Quenched by Boron Ate Complex and CF3I.
Content
1.Introduction
2.Radical-Induced 1,2-Migrations of Boron Ate Complexes
2.1 Radical-Induced 1,2-Boron Ate Migration to sp2 Carbons
2.2 Radical-Induced 1,2-Boron Ate Migration to sp3 Carbons
3. Summary and Outlook
31
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Other migration groups such as heteroatom group?
Heteroatom-centered radicals as a reactant partner?
Enantioselective process?
Summary and Outlook
33
Thanks For Your Attention
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