cross-electrophile couplingkanai/seminar/pdf/lit_t_wakaki_m2.pdfpotential mechanisms for...
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Cross-Electrophile
CouplingM2 Takayuki Wakaki
20150919
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Contents
1. Introduction
2. Cross-Electrophile Coupling
3. Cross-Electrophile Coupling ~co-catalyst system
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1. Introduction
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Cross-Coupling
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Cross-Coupling vs Reductive Cross-Coupling
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Cross Selectivity-Major Approach-
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Dr. Daniel J. Weix
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2. Cross-Electrophile
Coupling
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Initial Discovery of The Coupling of Aryl-I with Alkyl-I
Dual-ligand Ni catalyst system
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Substrate Scope
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Coupling of Alkyl-Br with Ar-Br or Ar-Cl
JACS, 2012, 134, 6146.11
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Substrate Scope of Aryl and Alkyl Bromides
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Chemoselectivity and Functional Group Compatibility
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Potential Mechanisms for Cross-Electrophile Coupling
JACS, 2013, 135, 16192. 14
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Mechanism A
1)Tolerance of functional groups
2)Direct insertion slower than reductive coupling. (left scheme)
3)Zn to TDAE nonmetallic reducing agent. (6 turnover number)
From above, A⇒× 15
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Mechanism B
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Mechanism C & D~ begin with Ar-Ni-I or Alkyl-Ni-I? ~
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Radical intermediate & Which one is more reasonable C or D?
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Proposed Mechanism
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Hypothesis for Self-Initiation
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3. Co-Catalyst System
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Co-Catalyst System
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Nickel-Catalyzed Regiodivergent Opening of Epoxides with Aryl Halides:
Co-Catalysis Controls Regioselectivity
J. Am. Chem. Soc. 2014, 136, 48.
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Substrate Scope
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Enantioselective Arylation of meso-Epoxides
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Substrate Scope
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Formation of [3, 3, 0]Bicycoocatanol Products
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Proposed Catalytic Cycle
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Coupling of Benzyl Mesylates with Ar-X
Problems (under their reported conditions)
Chem. Sci. 2015, 6, 1115.29
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Solution & Optimization
Mechanism based solution
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Optimization & Substrate Scope
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Multimetallic Catalysed Cross-coupling of Aryl
Bromides with Aryl Triflates
Nature, 2015, 524, 454–457.
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Selectivities of Nickel and Palladium
C) (dppp)PdCl2 (10 mol%)a) (dppp)PdCl2
and
(bpy)NiBr2 (10 mol%)
b) (bpy)NiBr2 (10 mol%)
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Conditions for the Multimetal-Catalyzed Cross-Ulmann Reaction
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Summary
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