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On the basis of the above experimental results, a mechanism has
been proposed as shown in Fig. 2. The reaction of the Cu precatalyst
with LiOtBu forms the catalytically active species Ⅰ. This complex
can easily undergo transmetalation with B2nep2 to generate
intermediateⅡ, followed by cis insertion of alkyne 1 to generate
species Ⅲ. Subsequent hydrolysis of Ⅲ with D2O can furnish the
monoborylation product B and copper species Ⅳ , which can be
regenerated by further cation exchange with LiOtBu. The copper
catalyst Ⅰ can undergo transmetalation with the formed
intermediate B to produce the stereoselective vinyl copper complex
Ⅴ. Further protonation of Ⅴ with D2O can yield the cis-selective
dideuteration products 2 and allow recovery of the copper species
Ⅳ.
6
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D
Bnep
R1
B2nep2
R2
tBuO Bnep
tBuO Bnep
B
8
9
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Bnep CuL
tBuO CuL
Ⅱ
D
Ⅰ
CuL
R1
R2
R1
OD
Li
R2
1
LiOtBu
CuL
Ⅴ
J. H. Kroll, N. M. Donahue, V. J. Cee, K. L. Demerjian, J. G.
Anderson, J. Am. Chem. Soc. 2002, 124, 8518.
DO
CuL
Ⅳ
Bnep
R1
10 (a) K. Harada, H. Urabe, F. Sato, Tetrahedron Lett. 1995, 36,
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For a boron-mediated palladium-catalysed hydrogenation and
deuteriation of alkynes using water, see: (f) S. P. Cummings, T.-
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R2
B2nep2
Ⅲ
D
D
2
Bnep
D2O
D2O
Bnep
R1
D
Bnep
R1
R1
R2
R2
R2
A
B
Figure 2 Proposed mechanism.
In summary, we developed an efficient copper-catalytic system
that is capable of selectively yielding deuterated semihydrogenation
of alkynes with heavy water to produce various thermodynamically
less stable cis-dideuterated olefins. The important features of this
approach are: practical and safe reaction conditions compared to the
existing methods, wide substrate scope, simple experimental
protocols and highly stereoselectivity. We believe that these
methods will simplify the synthesis and structural elaboration of d2-
deuterium-labeled cis-alkenes, which can be used in drug discovery. 12 J. Hu, X. Han, Y. Yuan, Z. Shi, Angew. Chem. Int. Ed. 2017, 56,
13342.
Acknowledgement:
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We thank the “1000-Youth Talents Plan”, the “Jiangsu Specially-
Appointed Professor Plan”, and the National Natural Science
Foundation of China (Grants 21672097).
Notes and references
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4 | J. Name., 2012, 00, 1-3
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