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Organic & Biomolecular Chemistry
Journal Name
ARTICLE
the desired products 6am and 6ja in good yields. Catalyst 1a
showed higher catalytic activity for the β-alkylation of 3a with 2a
than Ni(OAc)2(H2O)4/bis(diphenylphosphanyl)methane (dppm) at
115 °C. The latter facilitated an 85% yield of 6aa after 30 h.16
Acknowledgements
The authors thank the National Natural ScienDcOeI:F1o0u.1n0d39a/tCio9nOoBf00C4h1in8Aa
(21771131, 21471108, 21531006 and 21773163), the Natural
Science Foundation of Jiangsu Province (BK20161276), the State
Key Laboratory of Organometallic Chemistry of Shanghai Institute of
Organic Chemistry (2018kf-05), the "Priority Academic Program
Development" of Jiangsu Higher Education Institutions and
Scientific and Technologic Infrastructure of Suzhou (SZS201708).
We are grateful to the useful comments of the editor and reviewers.
Synthesis of quinoline. Our Ni(II) catalytic system also displayed
high activity for dehydrogenative cyclization of 2-aminobenzyl
alcohol with secondary alcohols to yield industrially useful
quinolines (Table 5). Various secondary alcohols gave the
corresponding products in 50-71% yield using 1a (5 mol % Ni) as the
catalyst, KOH (0.5 equiv.) as the base in toluene at 110 °C, under a
steady N2 flow for 24 h. Secondary alcohols (3a, 3b, 3c, 3h) with
electron-rich groups provided slightly higher yields than those with
electron-deficient substituents (3d-3g). Heteroatom-containing
alcohols such as 1-(pyridin-3-yl)ethan-1-ol, 1-(thiophen-2-yl)ethan-
1-ol reacted in moderate yield (8k in 65% yield and 8l in 61% yield).
References
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1a (5 mol% Ni)
KOH (0.5 equiv)
Ar2
OH
OH
NH2
Ar1
Ar2
+
N
Ar1
toluene (3 mL)
N2 flow, 110 o
C
8
3
7
N
N
N
X
8h:
8j:
8i:
61%
56%
8a:
8b:
8c:
8d:
8e:
8f:
X = H, 64%
X = Me, 67%
X = MeO, 70%
X = F, 52%
X = Cl, 57%
X = Br, 53%
X = CF3, 50%
4
N
N
8k:
71%
65%
N
8g:
5
6
N
S
N
Fe
8l:
61%
8m:
67%
Reaction conditions: 3 (1.2 mmol), 7 (1.0 mmol), 1a (5 mol% Ni), KOH (0.5 mmol),
toluene (3 mL), at 110 ºC under a N2 flow for 24 h, isolated yield.
Conclusions
In the work reported here, we have developed a well-defined
Ni(II)/thiolate cluster catalyst 1a for the efficient and
chemoselective C-C cross-coupling of secondary and primary
alcohols to generate α,β-unsaturated ketones, α-alkylated ketones
or β-alkylated secondary alcohols, just through simply controlling
reaction temperature, catalyst loading, reaction vessel closeness,
etc.. Diverse secondary and primary alcohols were well-tolerated to
furnish the corresponding products in good to excellent yields. This
catalytic system also displayed high activity for cross-coupling
annulation of 2-aminobenzyl alcohols with secondary alcohols to
yield quinolines under mild conditions. This methodology offers a
simple road to precisely control the multiple chemoselectivities of
the hydrogen-autotransfer catalysis and other complex systems by
carefully modifying reaction conditions.
7
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Conflicts of interest
There are no conflicts to declare.
10.1021/acs.chemrev.8b00306; (b) G. A. Filonenko, R. v.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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