Copper-catalyzed cyanothiolation to incorporate a sulfur-substituted quaternary carbon center

Article abstract of DOI:10.1039/c7sc02867a

Sulfur-containing nitriles have important research value in the life sciences due to their diverse biological activities resulting from the sulfur and cyano functional groups. Herein, a copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate α-arylthioalkanenitriles bearing sulfur-substituted quaternary carbon center atoms has been described. This novel protocol involves the procedure of copper carbene species promoting S-CN bond cleavage and C-CN/C-S bond reconstruction to introduce both sulfur and cyano groups onto a single carbon center. This cyanothiolation reaction will greatly enhance the synthetic utility of carbenoid species as new entries for the construction of diverse heteroatom-containing nitriles via cyanofunctionalization of metal-carbene species.

Full text of DOI:10.1039/c7sc02867a

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ISSN 2041-6539
EDGE ARTICLE
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DOI: 10.1039/C7SC02867A
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ꢁꢀꢆ&ꢈꢊ ꢌꢇꢅ+ꢃꢆ ꢌꢊꢆꢍꢊꢅꢓ
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ꢌꢃꢆꢌꢊꢅꢆꢔ ꢇꢁ ꢀꢍ 'ꢅꢃ*ꢀ%ꢊꢁ %ꢀꢅꢊꢌꢍ 'ꢇꢍ 5ꢇꢋꢁ ꢍꢃ ꢊꢆ ꢇꢆꢌꢊ ꢍ ꢊ
ꢁꢋꢆꢍ ꢊꢍꢀꢌ ꢇ''ꢈꢀꢌꢇꢍꢀꢃꢆꢁ ꢃꢎ ꢌꢇꢅ+ꢊꢆꢃꢀ% ꢁ'ꢊꢌꢀꢊꢁꢓ Lꢆ ꢍ ꢀꢁ ꢅꢊꢁ'ꢊꢌꢍꢔ ꢍ ꢊ
ꢌ ꢊꢏꢀꢌꢇꢈ +ꢃꢆ% ꢌꢈꢊꢇ*ꢇ&ꢊ ꢃꢎ ꢊꢍꢊꢅꢃꢇꢍꢃꢏ=ꢌꢃꢆꢍꢇꢀꢆꢀꢆ& ꢅꢊꢇꢌꢍꢇꢆꢍꢁ
@
ꢅꢊꢇꢅꢅꢇꢆ&ꢊꢏꢊꢆꢍ ꢃꢎ ꢁꢄꢈꢎꢃꢆꢀꢄꢏ ꢋꢈꢀ%ꢊꢔ 5 ꢊꢅꢊ ꢍ ꢊ ꢊꢏ'ꢈꢃꢋꢏꢊꢆꢍ ꢃꢎ ꢍ ꢊ
ꢆꢃ+ꢈꢊ ꢏꢊꢍꢇꢈ ꢌꢇꢍꢇꢈꢋꢁꢍ ꢀꢁ %ꢊꢏꢇꢆ%ꢊ%ꢓ {ꢄꢈꢎꢄꢅ"ꢌꢃꢆꢍꢇꢀꢆꢀꢆ& ꢌꢃꢏ'ꢃꢄꢆ%ꢁꢔ
ꢀꢆ*ꢃꢈ*ꢀꢆ& +ꢀꢇꢅꢋꢈ ꢁꢄꢈꢎꢀ%ꢊꢁ ꢇꢆ% ꢍ ꢊꢀꢅ ꢀ& ꢊꢅ ꢃꢒꢀ%ꢇꢍꢀꢃꢆ ꢃꢏꢃꢈꢃ&ꢄꢊꢁꢔ
B
%ꢀꢁ'ꢈꢇꢋ *ꢇꢅꢀꢊꢍꢀꢊꢁ ꢃꢎ +ꢀꢃꢈꢃ&ꢀꢌꢇꢈ ꢇꢆ% ' ꢇꢅꢏꢇꢌꢊꢄꢍꢀꢌꢇꢈ ꢇꢌꢍꢀ*ꢀꢍꢀꢊꢁꢔ ꢁꢄꢌ
ꢇꢁ ꢇꢆꢍꢀꢎꢄꢆ&ꢇꢈꢔ ꢇꢆꢍꢀ+ꢇꢌꢍꢊꢅꢀꢇꢈꢔ ꢇꢆ% ꢇꢆꢍꢀꢍꢄꢏꢃꢅꢇꢈ ꢇꢌꢍꢀ*ꢀꢍꢋꢓ Çꢃ ꢃꢄꢅ
;ꢆꢃ5ꢈꢊ%&ꢊꢔ %ꢀꢅꢊꢌꢍ ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ ꢃꢎ ꢏꢊꢍꢇꢈ"ꢌꢇꢅ+ꢊꢆꢊ ꢁ'ꢊꢌꢀꢊꢁ ꢍꢃ
ꢌꢃꢆꢁꢍꢅꢄꢌꢍ ꢁꢄꢈꢎꢄꢅ"ꢌꢃꢆꢍꢇꢀꢆꢀꢆ& ꢆꢀꢍꢅꢀꢈꢊꢁ ꢅꢊꢏꢇꢀꢆꢁ ꢄꢆꢊꢒ'ꢈꢃꢅꢊ%ꢓ .ꢇꢁꢊ% ꢃꢆ
Yꢃ [ꢁꢄꢅꢆꢁꢇꢅꢆ ꢅꢈ Cꢉꢊꢋꢇꢌꢅꢊꢁꢍ aꢅꢍꢃꢋꢉꢍꢁꢆ 9ꢊꢎꢌꢊꢃꢃꢆꢌꢊꢎ ꢅꢈ Dꢉꢁꢊꢎꢏꢅꢊꢎ tꢆꢅꢐꢌꢊꢋꢃꢑ {ꢋꢒꢅꢅꢍ
ꢅꢈ /ꢒꢃꢂꢌ!ꢇꢆ ꢁꢊꢏ /ꢒꢃꢂꢌꢋꢁꢍ 9ꢊꢎꢌꢊꢃꢃꢆꢌꢊꢎꢑ {ꢅꢉꢇꢒ /ꢒꢌꢊꢁ Üꢊꢌꢐꢃꢆ!ꢌꢇ ꢅꢈ Çꢃꢋꢒꢊꢅꢍꢅꢎ ꢑ
Dꢉꢁꢊꢎ$ꢒꢅꢉ %&'()' */ꢒꢌꢊꢁ+ꢀ 9,ꢂꢁꢌꢍ- ꢋꢃ.ꢉ./0!ꢋꢉꢇꢀꢃꢏꢉꢀꢋꢊꢑ 1ꢌꢁꢊꢎꢒꢈ0!ꢋꢉꢇꢀꢃꢏꢉꢀꢋꢊ
C
ꢃꢄꢅ 'ꢅꢊ*ꢀꢃꢄꢁ ꢁꢍꢄ%ꢀꢊꢁ ꢃꢆ ꢌꢃ''ꢊꢅ"ꢌꢇꢍꢇꢈꢋ:ꢊ% ꢌꢃꢄ'ꢈꢀꢆ& ꢅꢊꢇꢌꢍꢀꢃꢆꢁ ꢎꢃꢅ
*9ꢈꢊꢌꢍꢅꢃꢆꢀꢌ {ꢄ''ꢈꢊꢏꢊꢆꢍꢇꢅꢋ Lꢆꢎꢃꢅꢏꢇꢍꢀꢃꢆ (9{L) ꢇ*ꢇꢀꢈꢇ+ꢈꢊ, {ꢊꢊ 5hL, ꢑꢓ ꢑ!/0
ꢒꢑꢒꢒꢑꢑꢑꢑꢑꢒ
ꢍ ꢊ ꢎꢃꢅꢏꢇꢍꢀꢃꢆ ꢃꢎ ꢌꢇꢅ+ꢃꢆ" ꢊꢍꢊꢅꢃꢇꢍꢃꢏ +ꢃꢆ%ꢁꢔ ꢊꢅꢊꢀꢆꢔ 5ꢊ 'ꢅꢃ'ꢃꢁꢊ ꢇ
Ç ꢀꢁ ꢂꢃꢄꢅꢆꢇꢈ ꢀꢁ ꢉ Ç ꢊ wꢃꢋꢇꢈ {ꢃꢌꢀꢊꢍꢋ ꢃꢎ / ꢊꢏꢀꢁꢍꢅꢋ ꢐꢑꢒꢒ
Wꢀ bꢁꢂꢃꢓꢔ ꢐꢑ !ꢔ ꢈꢈꢔ "! # ꢉ
tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ

tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ
Chemical Science
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DOI: 10.1039/C7SC02867A
!wÇL/[9
Wꢎꢗꢌꢇꢅꢆ bꢅꢂꢁ
Çꢅꢙꢆꢁ 'ꢓ {ꢄ+ꢁꢍꢅꢇꢍꢊ {ꢌꢃ'ꢊ ꢃꢎ b"Çꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊꢁꢇꢓꢁ
ꢌꢃ''ꢊꢅ"ꢌꢇꢍꢇꢈꢋ:ꢊ% ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ ꢃꢎ b"ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊꢁ 5ꢀꢍ
ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢊꢁ ꢍꢃ ꢀꢆꢌꢃꢅ'ꢃꢅꢇꢍꢊ ꢁꢄꢈꢎꢄꢅ"ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% 8ꢄꢇꢍꢊꢅꢆꢇꢅꢋ ꢌꢇꢅ+ꢃꢆ
ꢌꢊꢆꢍꢊꢅ ꢍ ꢅꢃꢄ& ꢇ ꢌꢃ''ꢊꢅ ꢌꢇꢅ+ꢊꢆꢊ ꢁ'ꢊꢌꢀꢊꢁ 'ꢅꢃꢏꢃꢍꢀꢆ& {"/b +ꢃꢆ%
ꢌꢈꢊꢇ*ꢇ&ꢊ ꢇꢆ% /"/b0/"{ +ꢃꢆ% ꢅꢊꢌꢃꢆꢁꢍꢅꢄꢌꢍꢀꢃꢆ 'ꢅꢃꢌꢊꢁꢁ ({ꢌ ꢊꢏꢊ +)ꢓ
Ç ꢀꢁ 'ꢅꢃꢍꢃꢌꢃꢈ ꢀꢆꢁꢍꢇꢈꢈꢀꢆ& +ꢃꢍ ꢁꢄꢈꢎꢄꢅ ꢇꢆ% ꢌꢋꢇꢆꢃ &ꢅꢃꢄ'ꢁ ꢁꢀꢏꢄꢈꢍꢇꢆꢊꢃꢄꢁꢈꢋ
ꢀꢆ ꢃꢆꢊ"ꢁꢍꢊ' ꢏꢇꢆꢆꢊꢅ ꢍꢃ ꢇꢌꢌꢊꢁꢁ %ꢀ*ꢊꢅꢁꢊ 2"ꢇꢅꢋꢈꢍ ꢀꢃꢇꢈ;ꢇꢆꢊꢆꢀꢍꢅꢀꢈꢊꢁ 5ꢃꢄꢈ%
ꢎꢀꢆ% ꢀꢍꢁ 'ꢃꢍꢊꢆꢍꢀꢇꢈ ꢇ''ꢈꢀꢌꢇꢍꢀꢃꢆꢁ ꢀꢆ ꢍ ꢊ ꢎꢀꢊꢈ% ꢃꢎ ' ꢇꢅꢏꢇꢌꢊꢄꢍꢀꢌꢇꢈ ꢇꢆ%
ꢏꢇꢍꢊꢅꢀꢇꢈꢁ ꢁꢌꢀꢊꢆꢌꢊꢁꢓ
CuSCN (10 mol %)
DBU (1 equiv)
S
NNHTs
R1 CN
Ar
CN
+
Ar
R1
S
MeCN, 90 °C, N2
1
2a
3
CN
S
CN
CN
F
S
S
R
F
3ka, R = Me, 90%
3la, R = Cl, 87%
R
3ma, 78%
3aa, R = H, 91%
3ba, R = Me, 90%
3ca, R = MeO, 93%
3da, R = F, 85%
3ea, R = CF3, 90%
3fa, R = Br, 92%
CN
S
wꢁꢍꢗꢆꢓꢍ ꢅꢇꢖ ꢖꢃꢍꢄꢗꢍꢍꢃꢎꢇ
Çꢅꢙꢆꢁ ꢉꢋ h'ꢍꢀꢏꢀ:ꢇꢍꢀꢃꢆ ꢃꢎ ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆ ꢌꢃꢆ%ꢀꢍꢀꢃꢆꢁꢓꢁ
3ga, R = COOMe, 74%
3ha, R = CN, 92%
3ia, R = SO2Me, 86%
3ja, R = Ph, 85%
X-ray of 3na
3na, 95%
CN
S
CN
S
[Cu] (mol %)
CuTC (5)
CuSCN (5)
Cu(MeCN)4PF6 (5)
CuI (5)
2a (equiv)
1.0
1.0
base (equiv)
DBU (2)
DBU (2)
DBU (2)
DBU (2)
DBU (2)
DBU (2)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
solvent
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DCE
yield (%)b
entrya
O
S
70
58
21
3pa, 81%
1
2
3
4
5
6
7
8
9
3oa, 77%
R1 CN
NC
S
NC
S
1.0
S
1.0
1.0
1.0
1.0
1.5
2.0
1.5
1.5
36
55
76
83
94 (91)c
81
n.d.
52
CuTC (10)
3qa, R1 = iPr, 83%
3ra, R1 = Cyclopropyl, 89%
O
CuSCN (10)
CuSCN (10)
CuSCN (10)
CuSCN (10)
CuSCN (10)
CuSCN (10)
3sa, 87%
3ta, 92%
a
Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol), CuSCN (0.02 mmol), DBU (0.2
mmol) in 1.0 mL MeCN at 90 °C for 12 h. Isolated yield.
10
11
DMF
ꢇꢆ% E G ꢋꢀꢊꢈ%ꢁꢔ ꢅꢊꢁ'ꢊꢌꢍꢀ*ꢊꢈꢋꢓ aꢃꢅꢊꢃ*ꢊꢅꢔ ꢅꢊ'ꢈꢇꢌꢀꢆ& w &ꢅꢃꢄ'
5ꢀꢍ ꢁꢍꢊꢅꢀꢌꢇꢈꢈꢋ ꢀꢆ%ꢊꢅꢊ% ꢀꢁꢃ'ꢅꢃ'ꢋꢈ (ꢉ+) ꢃꢅ ꢌꢋꢌꢈꢃ'ꢅꢃ'ꢋꢈ (ꢉꢌ ꢇ%
ꢆꢃ ꢃ+*ꢀꢃꢄꢁ ꢀꢏ'ꢇꢌꢍ ꢃꢆ ꢍ ꢊ ꢋꢀꢊꢈ%ꢁ ꢇꢆ% ꢍ ꢊ ꢌꢃꢅꢅꢊꢁ'ꢃꢆ%ꢀꢆ&
'ꢅꢃ%ꢄꢌꢍꢁ ꢌꢃꢄꢈ% +ꢊ &ꢊꢆꢊꢅꢇꢍꢊ% ꢀꢆ &ꢃꢃ% ꢋꢀꢊꢈ%ꢁ ((+ꢅꢒ(ꢌꢅ)ꢓ Lꢍ ꢁ ꢃꢄꢈ%
+ꢊ ꢆꢃꢍꢊ% ꢍ ꢇꢍ 5 ꢊꢆ ꢄꢁꢀꢆ& ꢍ ꢊ b"ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊꢁ +ꢊꢇꢅꢀꢆ&
a
)
Reaction conditions: All reactions were performed with 1a (0.1 mmol), 2a, catalyst,
DBU in 0.5 mL solvent at 90 °C under nitrogen atmosphere for 12 h. GC-MS yield
using n-dodecane as an internal standard. n.d. = not detected. c Isolated yield.
b
ꢍꢊꢍꢅꢇ ꢋ%ꢅꢃꢆꢇ' ꢍ ꢇꢈꢊꢆꢊ
(ꢉꢍ) ꢇꢆ% ꢌ ꢅꢃꢏꢇꢆ (ꢉꢓ) ꢇꢁ ꢍ ꢊ
íꢊ ꢀꢆꢀꢍꢀꢇꢍꢊ% ꢃꢄꢅ ꢁꢍꢄ%ꢀꢊꢁ ꢄꢁꢀꢆ& ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆ +ꢊꢍ5ꢊꢊꢆ b"
ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊ ꢃꢎ ꢇꢌꢊꢍꢃ' ꢊꢆꢃꢆꢊ (ꢉꢅ) ꢇꢆ% ꢓꢑ ꢊ8ꢄꢀ* ꢃꢎ "ꢏꢊꢍ ꢋꢈ"@"
ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢃ+ꢊꢆ:ꢊꢆꢊ ('ꢅ) 5ꢀꢍ B ꢏꢃꢈ G /ꢄÇ/ ꢇꢆ% ꢐ ꢊ8ꢄꢀ* ꢃꢎ 5.Ü ꢀꢆ
ꢑꢓB ꢏ[ aꢊ/bꢓ Dꢅꢇꢍꢀꢎꢋꢀꢆ&ꢈꢋꢔ ꢍ ꢊ %ꢊꢁꢀꢅꢊ% 'ꢅꢃ%ꢄꢌꢍ (ꢅꢅ 5ꢇꢁ &ꢀ*ꢊꢆ ꢀꢆ
DꢑG ꢋꢀꢊꢈ% ꢇꢎꢍꢊꢅ ꢐ ꢇꢍ /ꢑ I/ ꢄꢆ%ꢊꢅ ꢆꢀꢍꢅꢃ&ꢊꢆ ꢇꢍꢏꢃꢁ' ꢊꢅꢊꢓ ëꢇꢅꢀꢃꢄꢁ
ꢍꢋ'ꢊꢁ ꢇꢆ% ꢈꢃꢇ%ꢀꢆ&ꢁ ꢃꢎ ꢌꢃ''ꢊꢅ ꢌꢇꢍꢇꢈꢋꢁꢍꢁ 5ꢊꢅꢊ ꢍ ꢊꢆ ꢁꢌꢅꢊꢊꢆꢊ% (Çꢇ+ꢈꢊ ꢔ
ꢊꢆꢍꢅꢀꢊꢁ "C)ꢔ ꢇꢆ% ꢍ ꢊ ꢋꢀꢊꢈ% ꢃꢎ (ꢅꢅ ꢀꢆꢌꢅꢊꢇꢁꢊ% ꢍꢃ DCG 5 ꢊꢆ ꢑ ꢏꢃꢈ G
ꢃꢎ /ꢄ{/b 5ꢇꢁ ꢄꢁꢊ% ꢇꢁ ꢌꢇꢍꢇꢈꢋꢁꢍ (ꢊꢆꢍꢅꢋ C)ꢓ Ç ꢊ ꢀꢆ*ꢊꢁꢍꢀ&ꢇꢍꢀꢃꢆ ꢃꢎ ꢍ ꢊ
ꢊꢎꢎꢊꢌꢍꢁ ꢃꢎ 'ꢅ ꢇꢆ% 5.Ü ꢈꢃꢇ%ꢀꢆ&ꢁ (ꢊꢆꢍꢅꢀꢊꢁ C"/) ꢅꢊ*ꢊꢇꢈꢊ% ꢍ ꢇꢍ 5 ꢊꢆ
ꢊꢏ'ꢈꢃꢋꢀꢆ& ꢓB ꢊ8ꢄꢀ* ꢃꢎ 'ꢅ ꢇꢆ% ꢊ8ꢄꢀ* ꢃꢎ 5.Üꢔ ꢍ ꢊ ꢋꢀꢊꢈ% ꢌꢃꢄꢈ% ꢅꢊꢇꢌ
/@G (ꢊꢆꢍꢅꢋ E)ꢓ Lꢍ 5ꢇꢁ ꢎꢃꢄꢆ% ꢍ ꢇꢍ %ꢀꢎꢎꢊꢅꢊꢆꢍ ꢁꢃꢈ*ꢊꢆꢍꢁ %ꢀ% ꢆꢃꢍ ꢇ*ꢊ
ꢏꢄꢌ ꢊꢎꢎꢊꢌꢍ ꢃꢆ ꢍ ꢊ ꢋꢀꢊꢈ% (ꢊꢆꢍꢅꢀꢊꢁ ꢑ" )ꢓ !%%ꢀꢍꢀꢃꢆꢇꢈꢈꢋꢔ ꢌꢃꢆꢍꢅꢃꢈ
ꢊꢒ'ꢊꢅꢀꢏꢊꢆꢍꢁ ꢁ ꢃ5ꢊ% ꢍ ꢇꢍ ꢆꢃ ꢅꢊꢇꢌꢍꢀꢃꢆ ꢃꢌꢌꢄꢅ ꢀꢆ ꢍ ꢊ ꢇ+ꢁꢊꢆꢌꢊ ꢃꢎ /ꢄ
ꢌꢇꢍꢇꢈꢋꢁꢍ ꢃꢅ +ꢇꢁꢊꢓ
ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁꢔ ꢍ ꢊ ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ ꢅꢊꢇꢌꢍꢀꢃꢆ &ꢇ*ꢊ ꢍ ꢊ
ꢌꢃꢅꢅꢊꢁ'ꢃꢆ%ꢀꢆ& 'ꢅꢃ%ꢄꢌꢍꢁ (ꢍꢅ ꢇꢆ% (ꢓꢅ ꢀꢆ EDG ꢇꢆ% /ꢐG ꢋꢀꢊꢈ%ꢁꢓ
Ç ꢊ ꢁꢍꢅꢄꢌꢍꢄꢅꢊ ꢃꢎ (ꢇꢅ 5ꢇꢁ ꢎꢄꢅꢍ ꢊꢅ ꢌꢃꢆꢎꢀꢅꢏꢊ% +ꢋ ó"ꢅꢇꢋ
ꢌꢅꢋꢁꢍꢇꢈꢈꢃ&ꢅꢇ' ꢀꢌ ꢇꢆꢇꢈꢋꢁꢀꢁꢓ
Çꢅꢙꢆꢁ (ꢓ {ꢄ+ꢁꢍꢅꢇꢍꢊ {ꢌꢃ'ꢊ ꢃꢎ Ç ꢀꢃꢌꢋꢇꢆꢇꢍꢊꢁꢇꢓꢁ
íꢀꢍ ꢍ ꢊ ꢃ'ꢍꢀꢏꢇꢈ ꢅꢊꢇꢌꢍꢀꢃꢆ ꢌꢃꢆ%ꢀꢍꢀꢃꢆꢁ ꢀꢆ ꢇꢆ%ꢔ 5ꢊ
ꢁꢄ+ꢁꢊ8ꢄꢊꢆꢍꢈꢋ ꢊꢒꢇꢏꢀꢆꢊ% ꢇ ꢁꢊꢅꢀꢊꢁ ꢃꢎ b"ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊꢁ ꢎꢃꢅ ꢍ ꢀꢁ
ꢍꢅꢇꢆꢁꢎꢃꢅꢏꢇꢍꢀꢃꢆ (Çꢇ+ꢈꢊ ꢐ)ꢓ .ꢃꢍ ꢊꢈꢊꢌꢍꢅꢃꢆ"ꢅꢀꢌ &ꢅꢃꢄ'ꢁ (aꢊꢔ aꢊh
ꢇꢆ% t ) ꢇꢆ% ꢊꢈꢊꢌꢍꢅꢃꢆ"'ꢃꢃꢅ &ꢅꢃꢄ'ꢁ (Cꢔ /C!ꢔ .ꢅꢔ /hꢐaꢊꢔ /b ꢇꢆ%
{hꢐaꢊ) ꢇꢍ ꢍ ꢊ 3ꢁꢆꢁ"'ꢃꢁꢀꢍꢀꢃꢆ ꢃꢎ ' ꢊꢆꢋꢈ ꢅꢀꢆ& 5ꢊꢅꢊ ꢍꢃꢈꢊꢅꢇꢍꢊ% ꢀꢆ
ꢍ ꢀꢁ ꢌꢃꢆ*ꢊꢅꢁꢀꢃꢆꢔ ꢇꢆ% ꢍ ꢊ ꢌꢃꢅꢅꢊꢁ'ꢃꢆ%ꢀꢆ& 'ꢅꢃ%ꢄꢌꢍꢁ ((ꢙꢅꢒ()ꢅ
)
5ꢊꢅꢊ &ꢀ*ꢊꢆ ꢀꢆ &ꢃꢃ% ꢍꢃ ꢊꢒꢌꢊꢈꢈꢊꢆꢍ ꢋꢀꢊꢈ%ꢁꢓ í ꢊꢆ ꢍ ꢊ ꢂꢃꢇꢁ"
ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% &ꢅꢃꢄ' 5ꢇꢁ ꢏꢊꢍ ꢋꢈ ((*ꢅ) ꢃꢅ ꢌ ꢈꢃꢅꢀ%ꢊ ((ꢆꢅ)ꢔ ꢍ ꢊ
ꢅꢊꢇꢌꢍꢀꢃꢆ &ꢇ*ꢊ ꢍ ꢊ %ꢊꢁꢀꢅꢊ% 'ꢅꢃ%ꢄꢌꢍꢁ ꢀꢆ /ꢑG ꢇꢆ% EDG ꢋꢀꢊꢈ%ꢁꢔ
ꢅꢊꢁ'ꢊꢌꢍꢀ*ꢊꢈꢋꢓ 5ꢀꢎꢈꢄꢃꢅꢃ"ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁ ꢌꢃꢄꢈ% ꢍꢅꢇꢆꢁꢎꢊꢅ ꢍꢃ
ꢍ ꢊ ꢌꢃꢅꢅꢊꢁ'ꢃꢆ%ꢀꢆ& 'ꢅꢃ%ꢄꢌꢍ (ꢂꢅ ꢀꢆ DEG ꢀꢁꢃꢈꢇꢍꢊ% ꢋꢀꢊꢈ%ꢓ Lꢍ ꢁ ꢃꢄꢈ%
+ꢊ ꢆꢃꢍꢊ% ꢍ ꢇꢍ ꢆꢇ' ꢍ ꢇꢈꢊꢆꢊ ꢇꢆ% ꢊꢍꢊꢅꢃꢌꢋꢌꢈꢀꢌ (ꢎꢄꢅꢇꢆ ꢇꢆ%
ꢍ ꢀꢃ' ꢊꢆꢊ) ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁ ꢄꢆ%ꢊꢅ5ꢊꢆꢍ ꢍ ꢊ ꢍꢅꢇꢆꢁꢎꢃꢅꢏꢇꢍꢀꢃꢆꢁ
ꢁꢏꢃꢃꢍ ꢈꢋꢔ ꢇꢎꢎꢃꢅ%ꢀꢆ& ꢍ ꢊ %ꢊꢁꢀꢅꢊ% 'ꢅꢃ%ꢄꢌꢍꢁ (ꢇꢅꢒ(ꢑꢅ ꢀꢆ /BGꢔ DDG
a Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol), CuSCN (0.02 mmol), DBU (0.2
mmol) in 1.0 mL MeCN at 90 °C for 12 h. Isolated yield.
Ç ꢊꢆꢔ ꢍ ꢊ ꢁꢄ+ꢁꢍꢅꢇꢍꢊ ꢁꢌꢃ'ꢊ ꢃꢎ ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢊꢁ 5ꢇꢁ ꢊꢒꢇꢏꢀꢆꢊ%
ꢇꢆ% ꢍ ꢊ ꢅꢊꢁꢄꢈꢍꢁ ꢇꢅꢊ ꢁ ꢃ5ꢆ ꢀꢆ Çꢇ+ꢈꢊ !ꢓ 9ꢈꢊꢌꢍꢅꢃꢆ"5ꢀꢍ %ꢅꢇ5ꢀꢆ&
ꢇꢆ% ꢊꢈꢊꢌꢍꢅꢃꢆ"%ꢃꢆꢇꢍꢀꢆ& &ꢅꢃꢄ'ꢁ 5ꢊꢅꢊ 5ꢊꢈꢈ ꢍꢃꢈꢊꢅꢇꢍꢊ% ꢃꢆ ꢍ ꢊ ꢇꢅꢋꢈ
' # Wꢀ bꢁꢂꢃꢓꢔ ꢐꢑ ꢐꢔ ꢈꢈꢔ "!
Ç ꢀꢁ ꢂꢃꢄꢅꢆꢇꢈ ꢀꢁ ꢉ Ç ꢊ wꢃꢋꢇꢈ {ꢃꢌꢀꢊꢍꢋ ꢃꢎ / ꢊꢏꢀꢁꢍꢅꢋ ꢐꢑꢒꢒ
tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ

tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ
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DOI: 10.1039/C7SC02867A
Wꢎꢗꢌꢇꢅꢆ bꢅꢂꢁ
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ꢅꢀꢆ&ꢁ ꢃꢎ ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢊꢁ ((ꢅꢄꢒ(ꢅꢏ)ꢓ !ꢏꢃꢆ& ꢍ ꢊꢏꢔ ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁ 5ꢀꢍ
ꢇꢈꢃ&ꢊꢆ &ꢅꢃꢄ'ꢁ ((ꢅꢄ ꢇꢆ% (ꢅꢏ) %ꢊꢈꢀ*ꢊꢅꢊ% ꢍ ꢊ ꢊꢒ'ꢊꢌꢍꢊ% 'ꢅꢃ%ꢄꢌꢍꢁ
ꢀꢆ ꢅꢊꢈꢇꢍꢀ*ꢊꢈꢋ ꢈꢃ5ꢊꢅ ꢋꢀꢊꢈ%ꢁ ꢃꢎ EEG ꢇꢆ% EꢐG ꢅꢊꢁ'ꢊꢌꢍꢀ*ꢊꢈꢋꢓ í ꢊꢆ ꢐ"
ꢏꢀ& ꢍ +ꢊ %ꢄꢊ ꢍꢃ ꢍ ꢊ ꢀꢆꢁꢍꢇ+ꢀꢈꢀꢍꢋ ꢃꢎ ꢍ ꢊ %ꢀꢇ:ꢃ ꢌꢃꢏ'ꢃꢄꢆ% ꢇꢍ ꢀ& ꢊꢅ
ꢍꢊꢏ'ꢊꢅꢇꢍꢄꢅꢊꢓ Lꢆ ꢌꢃꢆꢍꢅꢇꢁꢍꢔ 5 ꢊꢆ 5.Ü 5ꢇꢁ ꢇ%%ꢊ%ꢔ ꢍ ꢊ ꢋꢀꢊꢈ% ꢃꢎ (ꢅꢅ
5ꢇꢁ ꢀꢆꢌꢅꢊꢇꢁꢊ% ꢍꢃ B!G ({ꢌ ꢊꢏꢊ ꢐꢔ ꢊ8ꢓ ꢐ+)ꢔ ꢁꢄ&&ꢊꢁꢍꢀꢆ& ꢍ ꢇꢍ 5.Ü
'ꢅꢃ+ꢇ+ꢈꢋ ꢇꢌꢍꢊ% +ꢃꢍ ꢇꢁ ꢈꢀ&ꢇꢆ% ꢇꢆ% +ꢇꢁꢊ ꢍꢃ ꢎꢇꢌꢀꢈꢀꢍꢇꢍꢊ ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆꢓ
Iꢃ5ꢊ*ꢊꢅꢔ 5 ꢊꢆ ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆ 5ꢇꢁ ꢌꢃꢆ%ꢄꢌꢍꢊ% ꢇꢍ ꢅꢃꢃꢏ ꢍꢊꢏ'ꢊꢅꢇꢍꢄꢅꢊ
5ꢀꢍ 5.Ü ꢇ%%ꢊ%ꢔ 'ꢅ %ꢀ% ꢆꢃꢍ 'ꢇꢅꢍꢀꢌꢀ'ꢇꢍꢊ ꢀꢆ ꢍ ꢊ ꢌꢃꢆ*ꢊꢅꢁꢀꢃꢆ ({ꢌ ꢊꢏꢊ ꢐꢔ
ꢊ8ꢓ ꢐꢌ)ꢔ ꢍ ꢊꢅꢊꢎꢃꢅꢊꢔ ꢇ ꢀ& ꢊꢅ ꢊꢆꢊꢅ&ꢋ 5ꢇꢁ ꢅꢊ8ꢄꢀꢅꢊ% ꢎꢃꢅ ꢍ ꢊ ꢌꢈꢊꢇ*ꢇ&ꢊ ꢃꢎ
{"/b +ꢃꢆ% ꢀꢆ ꢍ ꢀꢁ ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ ꢅꢊꢇꢌꢍꢀꢃꢆꢓ
ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢃꢆꢇ' ꢍ ꢇꢈꢊꢆꢊ 5ꢇꢁ ꢄꢁꢊ% ꢇꢁ
ꢇ ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢔ ꢍ ꢊ
ꢌꢃꢅꢅꢊꢁ'ꢃꢆ%ꢀꢆ& 'ꢅꢃ%ꢄꢌꢍ (ꢅꢀ 5ꢇꢁ ꢀꢁꢃꢈꢇꢍꢊ% ꢀꢆ /BG ꢋꢀꢊꢈ%ꢓ Iꢃ5ꢊ*ꢊꢅꢔ
ꢍ ꢊ ꢋꢀꢊꢈ% ꢃꢎ (ꢅꢃ +ꢊꢇꢅꢀꢆ& 'ꢋꢅꢀ%ꢀꢆꢊ ꢅꢀꢆ& 5ꢇꢁ %ꢊꢌꢅꢊꢇꢁꢊ% ꢍꢃ B!Gꢔ
5 ꢀꢈꢊ ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢊꢁ ꢌꢃꢆꢍꢇꢀꢆꢀꢆ& ꢃꢍ ꢊꢅ ꢊꢍꢊꢅꢃꢌꢋꢌꢈꢊꢁ ꢁꢄꢌ ꢇꢁ ꢎꢄꢅꢇꢆꢔ
ꢍ ꢀꢃ' ꢊꢆꢊ ꢇꢆ% "ꢏꢊꢍ ꢋꢈꢀꢆ%ꢃꢈꢊ 5ꢊꢅꢊ ꢁꢄꢀꢍꢇ+ꢈꢊ ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁ
ꢌꢃꢆ*ꢊꢅꢍꢊ% ꢍꢃ ꢍ ꢊ %ꢊꢁꢀꢅꢊ% 'ꢅꢃ%ꢄꢌꢍꢁ ꢀꢆ &ꢃꢃ% ꢋꢀꢊꢈ%ꢁ ((ꢅ)ꢒ(ꢅꢆ)ꢓ
aꢃꢅꢊꢃ*ꢊꢅꢔ 5 ꢊꢆ ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢃꢌꢋꢌꢈꢃ ꢊꢒꢇꢆꢊ 5ꢇꢁ ꢄꢁꢊ% ꢀꢆ ꢍ ꢊ
ꢅꢊꢇꢌꢍꢀꢃꢆꢔ @ꢐG ꢀꢁꢃꢈꢇꢍꢊ% ꢋꢀꢊꢈ% ꢃꢎ 'ꢅꢃ%ꢄꢌꢍ (ꢅꢂ ꢌꢃꢄꢈ% +ꢊ ꢃ+ꢍꢇꢀꢆꢊ%ꢓ
Çꢅꢙꢆꢁ ,ꢓ Cꢃꢅꢏꢇꢍꢀꢃꢆ ꢃꢎ bꢀꢍꢅꢀꢈꢊ tꢅꢃ%ꢄꢌꢍꢁꢓꢁꢑꢄ
{ꢄꢀꢁꢂꢁ 'ꢋ aꢊꢌ ꢇꢆꢀꢁꢍꢀꢌ ꢁꢍꢄ%ꢀꢊꢁꢓ D/"a{ ꢋꢀꢊꢈ% ꢄꢁꢀꢆ& ꢊ"%ꢃ%ꢊꢌꢇꢆꢊ
ꢇꢁ ꢇꢆ ꢀꢆꢍꢊꢅꢆꢇꢈ ꢁꢍꢇꢆ%ꢇꢅ%ꢓ ꢆꢓ%ꢓ > ꢆꢃꢍ %ꢊꢍꢊꢌꢍꢊ%ꢓ
.ꢇꢁꢊ% ꢃꢆ ꢍ ꢊ ꢇ+ꢃ*ꢊ ꢊꢒ'ꢊꢅꢀꢏꢊꢆꢍꢇꢈ ꢅꢊꢁꢄꢈꢍꢁꢔ ꢇ ꢍꢊꢆꢍꢇꢍꢀ*ꢊ ꢏꢊꢌ ꢇꢆꢀꢁꢏ
5ꢇꢁ 'ꢅꢃ'ꢃꢁꢊ% ꢎꢃꢅ ꢍ ꢀꢁ ꢌꢃ''ꢊꢅ"ꢌꢇꢍꢇꢈꢋ:ꢊ% ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ ꢃꢎ b"
ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊ ꢀꢆ {ꢌ ꢊꢏꢊ !ꢓ Lꢆꢀꢍꢀꢇꢈꢈꢋꢔ ꢍ ꢊ %ꢀꢇ:ꢃ ꢁꢄ+ꢁꢍꢅꢇꢍꢊ ! ꢀꢁ
ꢅꢊꢈꢊꢇꢁꢊ% ꢁꢈꢃ5ꢈꢋ ꢎꢅꢃꢏ ꢍ ꢊ b"ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊ ꢀꢆ ꢍ ꢊ 'ꢅꢊꢁꢊꢆꢌꢊ ꢃꢎ 5.Üꢔ
5 ꢀꢌ 5ꢃꢄꢈ% ꢅꢊꢇꢌꢍ 5ꢀꢍ /ꢄL ꢍꢃ &ꢀ*ꢊ ꢍ ꢊ ꢌꢃ''ꢊꢅ ꢌꢇꢅ+ꢊꢆꢊ ꢁ'ꢊꢌꢀꢊꢁ .ꢓ
íꢊ ꢁ'ꢊꢌꢄꢈꢇꢍꢊ ꢍ ꢇꢍ ꢍ ꢊ &ꢊꢆꢊꢅꢇꢍꢀꢃꢆ ꢃꢎ 'ꢅꢃ%ꢄꢌꢍ ꢏꢀ& ꢍ +ꢊ ꢐꢌꢁ ꢍ5ꢃ
'ꢇꢍ ꢁꢓ Lꢆ 'ꢇꢍ ꢁꢔ ꢍ ꢊ ꢀꢆꢍꢊꢅꢇꢌꢍꢀꢃꢆ ꢃꢎ ꢍ ꢀꢃꢌꢋꢇꢆꢇꢍꢊ ' ꢇꢆ% ꢌꢃ''ꢊꢅ
ꢌꢇꢅ+ꢊꢆꢊ ꢁ'ꢊꢌꢀꢊꢁ . ꢈꢊꢇ%ꢁ ꢍꢃ ꢍ ꢊ ꢎꢃꢅꢏꢇꢍꢀꢃꢆ ꢃꢎ ꢌꢃ''ꢊꢅLLL ꢌꢇꢅ+ꢊꢆꢊ
a
Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol), CuSCN (0.02 mmol), DBU (0.2
mmol) in 1.0 mL MeCN at 90 °C for 12 h. b Isolated yield.
Lꢆꢍꢊꢅꢊꢁꢍꢀꢆ&ꢈꢋꢔ 5 ꢊꢆ ꢍ ꢊ ꢅꢆꢇꢒꢅ"ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% (ꢅ"ꢏꢊꢍ ꢋꢈ ꢇꢆ% ꢅ"ꢌ ꢈꢃꢅꢃ)
b"ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊꢁ 5ꢊꢅꢊ ꢄꢁꢊ% ꢇꢁ ꢍ ꢊ ꢁꢄ+ꢁꢍꢅꢇꢍꢊꢁꢔ ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆ &ꢇ*ꢊ
ꢍ ꢊ ꢆꢀꢍꢅꢀꢈꢊ 'ꢅꢃ%ꢄꢌꢍꢁ ((ꢗꢅ ꢇꢆ% (-ꢅ) ꢀꢆ / G ꢇꢆ% /BG ꢀꢁꢃꢈꢇꢍꢊ% ꢋꢀꢊꢈ%ꢁ
ꢀꢆꢁꢍꢊꢇ% ꢃꢎ ꢌꢋꢇꢆꢃꢍ ꢀꢃꢈꢇꢍꢀꢃꢆ 'ꢅꢃ%ꢄꢌꢍꢁ (Çꢇ+ꢈꢊ @ꢔ ꢊ8ꢓ )ꢓ íꢊ ꢁꢄꢁ'ꢊꢌꢍꢊ%
ꢍ ꢇꢍ ꢍ ꢊ ꢅꢊꢇꢌꢍꢀꢃꢆ ꢏꢀ& ꢍ ꢎꢀꢅꢁꢍ ꢄꢆ%ꢊꢅ&ꢃ ꢍ ꢊ ꢌꢋꢇꢆꢃ &ꢅꢃꢄ' ꢀꢆꢁꢊꢅꢍꢀꢃꢆ
'ꢅꢃꢌꢊꢁꢁ ꢇꢎꢍꢊꢅ ꢍ ꢊ ꢌꢈꢊꢇ*ꢇ&ꢊ ꢃꢎ {"/b +ꢃꢆ%ꢔ ꢇꢆ% ꢁꢄ+ꢁꢊ8ꢄꢊꢆꢍꢈꢋꢔ ꢍ ꢊ
ꢅꢊꢈꢊꢇꢁꢊ ꢃꢎ ꢁꢄꢈꢎꢄꢅ &ꢅꢃꢄ' 5ꢇꢁ 'ꢅꢃꢏꢃꢍꢊ% %ꢄꢊ ꢍꢃ ꢍ ꢊ ꢁ'ꢇꢌꢊ ꢀꢆ%ꢅꢇꢆꢌꢊ ꢃꢎ
ꢅꢆꢇꢒꢅ"ꢁꢄ+ꢁꢍꢀꢍꢄꢊꢆꢍꢁꢓ aꢃꢅꢊꢃ*ꢊꢅꢔ 5 ꢊꢆ ꢅꢆꢇꢒꢅ"ꢎꢈꢄꢃꢅꢃ"ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% b"
ꢍꢃꢁꢋꢈ ꢋ%ꢅꢇ:ꢃꢆꢊ 5ꢇꢁ ꢊꢏ'ꢈꢃꢋꢊ%ꢔ ꢅꢆꢇꢒꢅ"ꢍ ꢀꢃ' ꢊꢆꢋꢈ"ꢁꢄ+ꢁꢍꢀꢍꢄꢍꢊ% ꢆꢀꢍꢅꢀꢈꢊ
'ꢅꢃ%ꢄꢌꢍ (ꢊꢅ 5ꢇꢁ ꢇꢎꢎꢃꢅ%ꢊ% ꢀꢆ !/G ꢋꢀꢊꢈ% (Çꢇ+ꢈꢊ @ꢔ ꢊ8ꢓ ꢐ)ꢔ ꢁꢄ&&ꢊꢁꢍꢀꢆ&
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Chemical Science
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DOI: 10.1039/C7SC02867A
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Ç ꢀꢁ ꢂꢃꢄꢅꢆꢇꢈ ꢀꢁ ꢉ Ç ꢊ wꢃꢋꢇꢈ {ꢃꢌꢀꢊꢍꢋ ꢃꢎ / ꢊꢏꢀꢁꢍꢅꢋ ꢐꢑꢒꢒ
tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ

tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ
Chemical Science
Page 5 of 6
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DOI: 10.1039/C7SC02867A
Wꢎꢗꢌꢇꢅꢆ bꢅꢂꢁ
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/ꢒꢃꢂꢀ Lꢊꢇꢀ 9ꢏꢓꢔ ꢐꢑ Cꢔ 33ꢔ ꢐE@ꢑꢓ
Ç ꢀꢁ ꢂꢃꢄꢅꢆꢇꢈ ꢀꢁ ꢉ Ç ꢊ wꢃꢋꢇꢈ {ꢃꢌꢀꢊꢍꢋ ꢃꢎ / ꢊꢏꢀꢁꢍꢅꢋ ꢐꢑꢒꢒ
Wꢀ bꢁꢂꢃꢓꢔ ꢐꢑ !ꢔ ꢈꢈꢔ "! # 3
tꢈꢊꢇꢁꢊ %ꢃ ꢆꢃꢍ ꢇ%ꢂꢄꢁꢍ ꢏꢇꢅ&ꢀꢆꢁ

Chemical Science
Page 6 of 6
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DOI: 10.1039/C7SC02867A
CuI
RS CN
RS CN
• Inexpensive copper catalyst
• Readily available substrates
• Simple operation
NNHTs
R2
CuI
R2
DBU
R1
R1
R1 R2
Thiocyanation
in situ
• Good functional group tolerance
32 examples
up to 95% yield
A copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate α-arylthioalkanenitriles bearing
sulfur-substituted quaternary carbon center atoms has been achieved.