Formation of Methylene Linkage for N-Heterocycles: Sequential C-H and C-O Bond Functionalization of Methanol with Cosolvent Water

Article abstract of DOI:10.1021/acs.joc.9b00729

An iron-catalyzed methylene forming strategy is disclosed through sequential C-H and C-O bond functionalization of methanol with cosolvent water. This protocol provides an easy and novel access to methylene-tethered imidazo[1,2-a]pyridine and 2-aminopyridine analogues in a sustainable manner and represents a complementary approach to traditional methylene forming strategies.

Full text of DOI:10.1021/acs.joc.9b00729

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Article
Formation of Methylene Linkage for N-Heterocycles: Sequential C–
H and C–O Bond Functionalization of Methanol with Cosolvent Water
Na Li, Jinku Bai, Xiaolin Zheng, and Honghua Rao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00729 • Publication Date (Web): 15 May 2019
Downloaded from http://pubs.acs.org on May 15, 2019
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Formation of Methylene Linkage for N-Heterocycles: Sequential C–H
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INTRODUCTION
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entry Catalyst Oxidant
Solvent
Ligand
yield (%)b
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FeCp2
FeCp2
FeCp*2
dppf
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPdec
DTBP
MeOH
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44
75
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48
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31
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MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (8:2)
MeOH/H2O (6:4)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
MeOH/H2O (7:3)
-
3
-
4
5c
-
FeCl2
FeCl3
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
FeCp2
-
-
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CHP
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RESULTS AND DISCUSSION
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23c
24d
25e
26f
27
DCP
-
(BzO)2
BzOOBut
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
TBHPaq
-
-
-
-
-
58
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80
70
71
42
43
76
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42
80
85
72
-
-
L1
L2
L3
L4
L5
L6
L7
L8
L1
L1
L1
L1
L1
TBHPaq
59
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CONCLUSION
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EXPERIMENTAL SECTION
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ASSOCIATED CONTENT
Supporting Information
AUTHOR INFORMATION
Corresponding Author
Author Contributions
ǁ
Notes
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ACKNOWLEDGMENT
REFERENCES
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