Rhodium(III)-catalyzed selective C-H cyanation of indolines and indoles with an easily accessible cyano source

Article abstract of DOI:10.1002/adsc.201401152

The rhodium-catalyzed selective cyanation of C-H bonds of indolines and indoles with N-cyano-N-phenyl-para-methylbenzenesulfonamide is described. This protocol offers a facile access to C-7 cyanated indolines and C-2 cyanated indoles with high site selectivity and excellent functional group tolerance.

Full text of DOI:10.1002/adsc.201401152

UPDATES
DOI: 10.1002/adsc.201401152
À
Rhodium(III)-Catalyzed Selective C H Cyanation of Indolines
and Indoles with an Easily Accessible Cyano Source
Neeraj Kumar Mishra,a Taejoo Jeong,a Satyasheel Sharma,a Youngmi Shin,a
Sangil Han,a Jihye Park,a Joa Sub Oh,b Jong Hwan Kwak,a Young Hoon Jung,a
and In Su Kima,*
a
School of Pharmacy, Sungkyunkwan University, Suwon 440-746, Republic of Korea
Fax : (+82)-31-292-8800; e-mail: insukim@skku.edu
College of Pharmacy, Dankook University, Cheonan 330-714, Republic of Korea
b
Received: December 12, 2014; Revised: January 15, 2015; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201401152.
Abstract: The rhodium-catalyzed selective cyana-
tion of C H bonds of indolines and indoles with N-
tives. For example, Yu reported the Cu(II)-mediated
À
À
C H cyanation of arylpyridines with TMSCN or
cyano-N-phenyl-para-methylbenzenesulfonamide is
described. This protocol offers a facile access to C-7
cyanated indolines and C-2 cyanated indoles with
high site selectivity and excellent functional group
tolerance.
MeNO2 as CN sources.[8] Chang described the Pd(II)-
[9]
À
catalyzed cyanation of arene C H bonds and the
Cu(II)-mediated cyanation of electron-rich arenes[10]
using N,N-dimethylformamide (DMF) and ammonia
as a combined source for the cyano unit. Jiao demon-
strated the Pd(II)-catalyzed C-3 cyanation of indoles
and benzofurans employing DMF as both reagent and
solvent.[11] In addition, some studies on the palladium-
catalyzed and cooper-mediated direct cyanations of
aromatic compounds using non-metallic cyano sour-
ces, such as TMSCN,[12] isonitrile,[13] NH4HCO3/
DMSO,[14] tosyl cyanide[15] and AIBN,[16] have been
À
Keywords: C H activation; cyanation; indoles; in-
dolines; rhodium
Aromatic nitriles have been recognized as integral explored. Recently, Zhu demonstrated the practicable
structural motifs of pharmaceuticals, natural products, method for the formation of C-2 cyanated indoles
agrochemicals, and dyes.[1] The nitrile moiety has also using readily available MeCN as a cyanating agent in
served as a versatile synthetic precursor for the for- the presence of a copper salt.[17]
mation of aldehydes, ketones, amines, amides, carbox-
The reagent N-cyano-N-phenyl-para-methylbenze-
ylic acids, and heterocycles.[2] Traditional approaches nesulfonamide (NCTS) can be easily prepared from
for the synthesis of aromatic nitriles rely on Sandmey- phenylurea and para-toluenesulfonyl chloride via
er reactions[3] of aryldiazonium salts and Rosenmund– a single-step process.[18] In 2011, Wang first reported
von Braun reactions,[4] which have inherent limitations the Lewis acid-catalyzed C H cyanation of indoles
including the stoichiometric use of metal cyanides and and pyrroles at the C-3 position with NCTS as a new
harsh reaction conditions as well as the generation of electrophilic cyanating agent.[19] Fu[20] and Anbara-
hazardous HCN by-products. Aryl nitriles can also be san,[21] independently, reported the Rh(III)-catalyzed
À
À
prepared from aryl amides, aryl oximes, benzylic direct C H cyanations of oximes and arylpyridines
amines, and benzylic alcohols by using conventional with NCTS in 2013. Shortly afterwards, aryl phos-
conditions.[5] Alternative methods are the transition phates, benzamides and azobenzenes were also inves-
metal-catalyzed cyanation of aryl halides or arylbor- tigated as directing groups in the Rh(III)- or Ru(II)-
onic acids with nucleophilic nitrile sources, such as catalyzed cyanation reactions using NCTS.[22] During
metal cyanide salts [CuCN, KCN, NaCN, ZnCN, the preparation of our manuscript, Ackermann[23] and
K3Fe(CN)6], TMSCN, and acetone cyanohydrins.[6]
Glorius,[24] respectively, demonstrated the Co(III)-cat-
À
Recently, a great deal of effort has been devoted to alyzed selective C H cyanation of arenes and hetero-
À
the direct cyanation of arene C H bonds with non- arenes with NCTS.
metallic nitrile equivalents.[7] The selective cyanation
The indoline nucleus is a ubiquitous structural core
À
of C H bonds might be the most economic and and is widely found in heterocyclic compounds with
benign route to the preparation of aryl nitrile deriva- biological and medicinal applications.[25] In particular,
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Table 1. Optimization of the reaction conditions.[a]
Entry Catalyst
Additive
Solvent
Yield
[%][b]
1
2
3
4
5
6
7
8
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
Cu(OAc)2 DCE
32
61
65
40
30
46
30
10
AgOAc
NaOAc
KOAc
DCE
DCE
DCE
DCE
DCE
THF
MeCN
toluene
t-AmOH 10
DMF
DCE
DCE
DCE
DCE
CsOAc
[Ru(p-cymene)Cl2]2 NaOAc
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
9
N.R.
10
11
12[c]
13
14[d]
15[e]
N.R.
10
24
50
77
À
Scheme 1. Catalytic C H functionalization of indolines at
the C-7 position.
NaOAc
NaOAc
many pharmaceutical agents include the C-7 substitut-
ed indoline framework.[26] The installation of the CN
group into bioactive molecules may dramatically
modify their biological properties. Recently, the di-
recting group-assisted C-7 functionalizations of indo-
lines has been an area of intensive research with the
aim to override the inherent selectivity of indoles.[27]
In this context, acylation, arylation, alkenylation, al-
kylation, and amidation reactions were developed
(Scheme 1).
[a]
Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), catalyst
(5 mol%), AgSbF6 (20 mol%), additive (30 mol%), sol-
vent (1 mL) at 1308C for 24 h in pressure tubes.
Yield of product isolated by flash column chromatogra-
[b]
phy.
[c]
[d]
[e]
Without AgSbF6.
2 (0.3 mmol, 1.5 equiv.).
40 h.
afford 3a, albeit in relatively low yield (Table 1,
In 1995, Roduit and Wellig first described the for- entry 6). Further screening of solvents under other-
mation of 7-cyanoindoline from indoline with trichlor- wise identical conditions revealed that DCE was the
oacetonitrile as a cyanating agent in the presence of most effective solvent for this coupling reaction
a stoichiometric amount of BCl3.[28] In this precedent (Table 1, entries 7–11). Exclusion of either AgSbF6 or
report, only one example is given for the C-7 cynation NaOAc resulted in a significantly decreased forma-
reaction. Despite these advances, there has been no tion of the desired product 3a (Table 1, entries 12 and
À
report on a catalytic C H cyanation at the C-7 posi- 13). A decreased loading of the cyanide source 2,
tion of indolines and indoles. Herein, we described under otherwise identical conditions, led to a relatively
À
a facile approach for the C-7 selective C H cyanation decreased formation of 3a (Table 1, entry 14). Finally,
of indolines with NCTS as a user-friendly cyanation we observed that a longer reaction time provided op-
reagent. It is noteworthy that the formed C-7 cyanat- timal results for the C-7 cyanation of N-pivaloylindo-
ed indolines can be readily transformed into C-7 cya- line (Table 1, entry 15).
nated indoles under oxidative conditions.
To explore the substrate scope and limitations,
We initiated our investigation by varying the reac- a range of indolines was tested under the optimal re-
À
tion conditions for the envisioned C H cyanation of action conditions (Table 2). Other carbonyl or carba-
N-pivaloylindoline 1a with NCTS (2), and selected re- moyl directing groups 1b–1d were found to be effec-
sults are summarized in Table 1.
tive in the C-7 cyanation reaction of indolines. The cy-
Initial experiments indicated that a cationic Rh cat- anation reactions of C-2, C-3 or C-4 substituted N-
alyst in the presence of Cu(OAc)2 in DCE solvent at pivaloylindolines 1e and 1g–1j provided our desired
1308C can promote the coupling of 1a and 2 to pro- C-7 cyanated products 3e and 3g–3j in moderate to
vide the cyanated indoline 3a in 32% yield (Table 1, good yields. However, the cyanation of C-5 substitut-
entry 1). After screening a range of acetate additives, ed indolines 1f, 1k and 1l was found to be relatively
NaOAc was found to exhibit the highest reactivity less efficient under the current reaction conditions.
(Table 1, entries 2–5). Also, a cationic Ru catalyst en-
With the results on C-7 cyanation of indolines in
abled the desired cyanation reaction to proceed to hand, we further explored the C-2 selective cyanation
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Rhodium(III)-Catalyzed Selective C H Cyanation of Indolines and Indoles
Table 2. Scope of the C-7 cyanation of indolines.[a,b]
Table 3. Scope of the C-2 cyanation of indoles.[a]
[a]
[a]
Reaction conditions: 4a–4j (0.2 mmol), 2 (0.4 mmol),
Reaction conditions: 1a–1l (0.2 mmol), 2 (0.4 mmol),
[RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%), NaOAc
(30 mol%), DCE (1 mL) at 1108C for 20 h in pressure
tubes.
Yield of product isolated by flash column chromatogra-
phy.
[RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%), NaOAc
(30 mol%), DCE (1 mL) at 1308C for 40 h in pressure
tubes.
Yield of product isolated by flash column chromatogra-
phy.
[b]
[b]
of biologically active heterocycles with a removable 3a (58%) and 5a (95%), respectively (Scheme 2). To
pyrimidine directing group (Table 3). To our delight, demonstrate the utility of C-7 cyanated indolines,
indole 4a was efficiently coupled with NCTS (2) cleavage of the N-pivaloyl group of 3a under basic
under very similar reaction reaction conditions to pro- conditions was first attempted to afford free-(NH)-in-
vide C-2 cyanated indole 5a in 97% yield. In addition, doline 6a in 62% yield concomitant with the hydroly-
indoles 4b–4f bearing electron-rich and electron-defi- sis of a nitrile group. In addition, oxidation of 3a was
cient groups (OMe, NO2, CN, Cl and Me) on the aro- performed by using of DDQ to deliver the C-7 cya-
matic ring were found to be good substrates in this nated indole 6b in 65% yield. Meanwhile, we also car-
catalytic transformation. Notably, the sterically more ried out the deprotection of a pyrimidyl directing
congested C-3 substituted indole 4g delivered the de- group on C-7 cyanated indole 5a (Scheme 3). Treat-
sired cyanated product 5g with an excellent yield ment of 5a with NaOEt in DMSO at 1108C afforded
upon isolation. However, indole 4h with an ester 1H-indole-2-carbonitrile (7a) in 96% isolated yield,
moiety at the C-3 position displayed a relatively de- which is the key precursor for pharmaceutical
creased reactivity. Furthermore, carbazole 4i and pyr- agents.[29,30]
role 4j also participated in this catalytic cyanation re-
action to furnish the monocyanated products 5i and 5j tion reaction, H/D exchange experiments using indo-
in almost quantitative yields. line 1a and indole 4a were performed (Scheme 4).
To gain some mechanistic insights into this cyana-
The scale-up reactions of indoline 1a and indole 4a When MeOD was added to the reaction mixtures, re-
were performed under the standard reaction condi- markable H/D exchanges of recovered deuterio-1a
tions to afford the corresponding cyanated products and deuterio-4a were observed, which is indicative of
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Scheme 2. Scale-up experiments and synthetic transforma-
tions.
Scheme 4. H/D exchange and KIE experiments.
the reversible metalation–proto(deutero)demetalla-
tion process. Next, kinetic isotope effect (KIE) ex-
Based on our mechanistic studies, a possible cata-
periments on indolines (1a and deuterio-1a) and in- lytic cycle was proposed as shown in Scheme 5. First,
doles (4a and deuterio-4a) with 2 were carried out treatment of [RhCp*Cl2]2 with AgSbF6 and NaOAc
under the standard reaction conditions, which resulted generate the reactive cationic Rh(III) catalyst A,
À
in the KIE values (kH/kD) of 2.76 and 2.84, respective- which undergoes a reversible C H metallation with
À
ly, thus indicating that C H cleavage might be in- 1a to yield the cyclometallated complex B. Subse-
volved in the rate-limiting step.[31]
quent coordination of NCTS (2) with B provides in-
Scheme 3. Removal of a directing group and its application.
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Rhodium(III)-Catalyzed Selective C H Cyanation of Indolines and Indoles
Scheme 5. Proposed reaction mechanism.
termediate C, followed by insertion of the CN group
into the C(sp ) Rh bond generating the key inter-
mediate D. Then rearrangement of D delivers the
cyanated product 3a and rhodium species E, which
undergoes ligand exchange to afford the active rhodi-
um species A.
Representative Procedure for C-2 Cyanation of N-(2-
Pyrimidinyl)indoles with NCTS
2
À
To an oven-dried sealed tube charged with N-(2-pyrimidinyl)-
indole (4a) (39.1 mg, 0.2 mmol, 100 mol%), [RhCp*Cl2]2
(6.2 mg, 0.01 mmol, 5 mol%), AgSbF6 (13.7 mg, 0.04 mmol,
20 mol%), and NaOAc (4.9 mg, 0.06 mmol, 30 mol%) in
DCE (1 mL) was added NCTS (2) (108.9 mg, 0.4 mmol,
In conclusion, we have described an efficient
method for the rhodium-catalyzed direct C-7 or C-2 200 mol%). The reaction mixture was allowed to stir at
1108C for 20 h, and then cooled to room temperature. The
reaction mixture was diluted with EtOAc (3 mL) and con-
centrated under vacuum. The residue was purified by flash
column chromatography (n-hexanes/EtOAc=10:1) to afford
5a; yield: 42.9 mg (97%).
cyanations of highly substituted indolines or indoles
with NCTS as the non-metallic cyano group source.
These protocols allow the generation of an array of
cyanated indoles, which are known to be crucial scaf-
folds of biologically active compounds.
Acknowledgements
Experimental Section
This work was supported by the National Research Founda-
tion of Korea (NRF) grant funded by the Korean Govern-
Representative Procedure for C-7 Cyanation of N-
Pivaloylindolines with NCTS
ment
(Nos.
2013R1A2A2A01005249
and
2014R1A1A2056809).
To an oven-dried sealed tube charged with N-pivaloylindo-
line (1a) (40.6 mg, 0.2 mmol, 100 mol%), [RhCp*Cl2]2
(6.2 mg, 0.01 mmol, 5 mol%), AgSbF6 (13.7 mg, 0.04 mmol,
20 mol%), and NaOAc (4.9 mg, 0.06 mmol, 30 mol%) in References
DCE (1 mL) was added NCTS (2) (108.9 mg, 0.4 mmol,
200 mol%). The reaction mixture was allowed to stir at
1308C for 40 h, and then cooled to room temperature. The
reaction mixture was diluted with EtOAc (3 mL) and con-
centrated under vacuum. The residue was purified by flash
column chromatography (n-hexanes/EtOAc=10:1) to afford
3a; yield: 35.2 mg (77%).
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UPDATES
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Rhodium(III)-Catalyzed Selective C H Cyanation of
Indolines and Indoles with an Easily Accessible Cyano
Source
7
Adv. Synth. Catal. 2015, 357, 1 – 7
Neeraj Kumar Mishra, Taejoo Jeong, Satyasheel Sharma,
Youngmi Shin, Sangil Han, Jihye Park, Joa Sub Oh,
Jong Hwan Kwak, Young Hoon Jung, In Su Kim*
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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