Visible light mediated desilylative C(sp2)-C(sp2) cross-coupling reactions of arylsilanes with aryldiazonium salts under Au(i)/Au(iii) catalysis

Article abstract of DOI:10.1039/c8cc03925a

Desilylative C(sp²)-C(sp²) cross-coupling reactions of arylsilanes with aryldiazonium salts under Au(i)/photoredox catalysis have been reported. The addition of Cu-salts as catalysts was found to be crucial for the success of this tr

Full text of DOI:10.1039/c8cc03925a

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Visible Light Mediated Desilylative C(sp2)-C(sp2) Cross-Coupling
Reactions of Arylsilanes with Aryldiazonium Salts under
Au(I)/Au(III) Catalysis
Received 00th January 20xx,
Accepted 00th January 20xx
Indradweep Chakrabarty,ab Manjur O. Akram,ab Suprakash Biswasc and Nitin T. Patil*c
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract. Desilylative C(sp2)-C(sp2) cross-coupling reactions of catalysis (Scheme 1b).15 To further explore the potential of
arylsilanes with aryldiazonium salts under Au(I)/photoredox organosilanes and as a part of our ongoing interest in Au(I)/Au(III)
catalysis has been reported. The addition of Cu-salts as catalysts catalysis,16 we envisioned that C(sp2)-C(sp2) cross coupling reactions
was found to be crucial for the success of this transformations.
between arylsilanes and aryldiazonium salts could be achieved
under merged gold/photoredox catalysis (Scheme 1c). However,
under established reaction conditions,14,15 the reaction of 2-
(trimethylsilyl)-benzofuran (1a) and p-Cl-C6H4N2BF4 (2a) did not
Over the last few years, the chemistry of UV light mediated
photoredox gold catalysis1 and merged gold/visible light
photoredox catalysis2 have emerged as a powerful tool for the
development of novel organic transformations. Especially, the
research group of Glorius3 and Toste4 have shown the potential of
this strategy in cross-coupling reactions involving Au(I)/Au(III)
catalysis.5 The key aspect in the mechanism is the step-wise
oxidation of Au(I)-catalysts to Au(III)-species by an aryl radical
[generated in situ via the photocatalytic decomposition of
aryldiazonium salt (ArN2X).6 Unlike other external oxidant aided
gold(I)-catalyzed cross-coupling reactions,7 such strategies operates
under mild reaction conditions. Several other research groups also
exploited the potential of this strategy for either arylative
difunctionalization of C−C mulꢀple bonds8 or cross-coupling
reactions involving C-C9 and C-P10 bond formation.11
work. Our efforts to screen
a
variety of gold catalysts and
failed.17
After several
photocatalysts (Ru) were all
experimentations, we found that the addition of catalytic amounts
of copper is the key for obtaining the desired cross-coupled
product. Herein, we report the detailed investigation on the
development of visible light mediated desilylative cross-coupling
reactions of arylsilanes and aryldiazonium salts under Au(I)/Au(III)
catalysis. Be noted that the role of Cu salts have been extensively
studied in the Pd-catalyzed reactions;18 however, to the best of our
knowledge, such role of copper has never been reported in the
gold-catalyzed cross-coupling reactions.
In most of these cross-coupling reactions, the choice of
nucleophilic coupling partner plays a crucial role. The coupling
partner should be compatible not only with diazonium salts12 but
also with the photo-catalyst and/or light. Though, organosilanes
have earned reputation as an attractive coupling partner, the use of
strong oxidants limits its attractiveness in gold-catalyzed cross-
coupling reactions.13 In 2016, Toste and coworkers disclosed gold-
catalyzed cross-coupling reactions of alkynyltrimethylsilanes with
ArN2X under merged gold/photoredox catalysis (Scheme 1a).14 Very
recently, we reported the cross-coupling reaction of aryl diazonium
salts with allyltrialkylsilanes utilizing merged gold/photoredox
Scheme 1. Desilylative cross-coupling reactions under merged gold/
photoredox catalysis: known and present work
We commenced our optimization studies with 1a and 2a (2
equiv) in presence of 10 mol% of Ph3PAuCl, 2.5 mol% of
[Ru(bpy)3(PF6)2] and 2 equiv of K2CO3 in degassed 0.1 M CH3CN
under the irradiation of 23 W CFL bulb (Table 1, entry 1). After we
identified the essential role of Cu salts (entry 2) in the coupling
reaction, we opted to screen various other Cu catalysts (entries 3-
8). Gratifyingly, the yield of 3a was improved (65%) when 20 mol%
Cu(MeCN)4BF4 was used (entry 7). Screening of various Au(I)
catalysts by keeping Cu(MeCN)4BF4 and [Ru(bpy)3(PF6)2] stationary
did not improve the yield of 3a (entries 9-14).17 Other solvents
aDivision of Organic Chemistry, CSIR - National Chemical Laboratory, Dr. Homi
Bhabha Road, Pune - 411 008, India.
bAcademy of Scientific and Innovative Research (AcSIR), New Delhi - 110 025, India.
cDepartment of Chemistry, Indian Institute of Science Education and Research
Bhopal, Bhauri, Bhopal - 462 066, India. Email: npatil@iiserb.ac.in
Supporting information for this article is given via
a link at the end of the
document. Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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(DCM, MeOH, THF, toluene) and bases (Na2CO3, Cs2CO3, NaOAc, provided products 3n, 3o and 3p in 69, 63 and 65% yields,
KOAc, NaOMe, KOtBu, NaOH etc.) found to be detrimental for the respectively. Electron withdrawing groups like -CN and -NO2 gave
reaction.17 The absence of either catalyst (Au, Ru, Cu) or light does 3q and 3r in good yields (78 and 54%). Conversely, in case of
not result in the product formation, indicating that the presence of electron donating -OMe group, product 3s was obtained in lower
each catalyst is essential.17
yield (32%). Similar set of results were obtained when we varied the
substituents at the ortho-position of the diazonium salts. For
example, diazonium salts containing -F, -Br, -I, -CN and -NO2
substituents afforded 3t-3x in excellent yields (68-88%). However,
diazonium salts containing electron donating -OMe group lead to
poor conversion (3y, 9%) and this observation was found to be
consistent with previously described cases (3m and 3s). The
sterically hindered diazonium salts, i.e. 2,4,6-trimethylphenyl
diazonium salt 1aa also gave the 3z in 75% yield. When we switched
to di and tri-substitution in the diazonium salts, desired products
were obtained in moderate to good yields (3aa-3ad, 63-72%).
Interestingly, heterocyclic scaffold like N-tosylated indole derived
diazonium salt was also well tolerated under the optimized reaction
conditions to give 3ae in 65% yield. Next, when 1g was treated with
aryldiazonium salts bearing -CN and -Br groups, products 3af and
3ag were obtained in moderate yields (52 and 57% yields). Next, we
demonstrated the scalability of our approach by performing the
reaction on 1 mmol scale of 1a. Notably, the yield remained
unaffected and product 3a was isolated in 70% yield.
Table 1. Optimization of reaction conditionsa
entry
1
[Au(I)] cat.
Ph3PAuCl
[Cu] cat.
--
CuI
CuBr
CuCl
yield (%)b
NR
30
2
Ph3PAuCl
3
Ph3PAuCl
45
40
39
50
65
61
NR
NR
10
4
Ph3PAuCl
5
Ph3PAuCl
Cu(OTf)2
Cu(OAc)2
6
Ph3PAuCl
7
Ph3PAuCl
Cu(MeCN)4BF4
Cu(MeCN)4PF6
Cu(MeCN)4BF4
Cu(MeCN)4BF4
Cu(MeCN)4BF4
Cu(MeCN)4BF4
Cu(MeCN)4BF4
Cu(MeCN)4BF4
8
Ph3PAuCl
9
IPrAuCl
10
11
12
13
14
CyJohnPhosAuCl
(C6F5)3PAuCl
(p-OMeC6H4)3PAuCl
Ph3PAuOTfc
17
14
21
c
Ph3PAuNTf2
Table 2. Scope with arylsilanes and aryldiazonium saltsa,b
aReaction conditions: 0.1 mmol 1a, 0.2 mmol 2a, 10 mol% [Au(I)]
cat., 2.5 mol% [Ru(bpy)3(PF6)2], 20 mol% [Cu] cat., 2 equiv K2CO3,
CH3CN (0.1 M), rt, 24 h. bIsolated yields. cGenerated in situ by
mixing equimolar amount of Ph3PAuCl and AgX (X = OTf, NTf2). NR =
no reaction.
With the optimized reaction conditions in hand (Table 1, entry
7), we explored the scope of the transformation using various aryl
trimethylsilane (1) and aryldiazonium salts (2) (Table 2). The
reaction was found to be faintly general irrespective of the
substituents present in the heteroaromatic(aryl)silanes. For
example, 3-methyl-2-trimethylsilyl-benzofuran (1b), 2-trimethylsilyl-
benzothiophene (1c) provided products 3b and 3c in 69 and 65%
yields, respectively. Further, N-Boc-protected 2-trimethylsilyl
indoles 1d and 1e reacted smoothly with 2a under optimized
reaction conditions to give 3d and 3e in 59 and 65% yields,
respectively. Similarly, N-tosyl-2-trimethylsilylindole (1f) gave the 3f
in 69% yield. Next, the tolerance of various arylsilanes was
examined. It is found that only electron withdrawing arylsilanes
such as 1-acetyl-4-trimethyl(phenyl)silane (1g) is suitable giving 3g
in 63% yields. We then sought to explore the wider potential of the
reaction with respect to aryldiazonium salts. For instance, the
reaction worked well in case of aryldiazonium salts containing -F, -
Br and -I substituents at the para-position giving 3h, 3i and 3j in
good yields (61-67%). The electronic nature of the diazonium salts
seemed to play a crucial role. For example, diazonium salts bearing
electron withdrawing -CO2Et and -NO2 gave the corresponding
cross-coupled products 3k and 3l in 62 and 70% yields, respectively.
On the other hand, diazonium salt bearing electron donating -OMe
group gave 3m only in 25% yield. Next, substituents at the meta
position of the aryldiazonium salts were varied. For instance,
aryldiazonium salts containing halo groups such as -F, -Cl and -Br
aReaction conditions: 0.20 mmol 1, 0.40 mmol 2, 10 mol%
Ph3PAuCl, 2.5 mol% [Ru(bpy)3(PF6)2], 20 mol% Cu(MeCN)4BF4, 2
equiv K2CO3, CH3CN (0.1 M), rt, 24 h. bIsolated yields. cNMR yield.
2 | J. Name., 2012, 00, 1-3
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To determine the effect of silyl group; substituted arylsilanes like chain mechanism was discarded based on the quantum yield
1a', 1a'' and 1a''' were prepared and examined under the optimized calculations.17
reaction conditions (Scheme 2). Pleasingly in all the cases, 3a was
Ph3P Ar2
obtained in good to moderate yields (59-65%).
A
Ar1-SiMe3
[RuII]
2a
Cu(I)
Scheme 2. Effect of bulk of silanes
Cl
[RuII]*
L
AuIII Ar2
Ar2N2BF4
III
1a
[RuIII]
Ar1-Cu(I)
Radical
ArN2BF4
chain
[Ar2] N2 BF4
II
Cl
AuII Ar2
Cl
L
G
cata
old
lysis
Ar2
Ar1
=
L
AuIII
Ar1 IV
Ar2
=
Next, we became curious to know the effect of counter anions
associated with diazonium salts (Scheme 3). Hence, we prepared
Ar
Cl
−
diazonium salts bearing counter anions such as PF6− (2a'), O(CO)CF3
O
L
AuI Cl
I
Ar1 Ar2
3a
(2a'') and OTs− (2a''') and subjected to optimized reaction
conditions. While 2a''' was found to be unsuitable, 2a' and 2a''
reacted with 1a giving 3a in 62 and 41% yields, respectively. Though
the counteranions were found to have immense effect on the
reaction outcome, their exact role in the catalytic cycle is not clear
yet.
L = PPh3
Scheme 4. A plausible reaction mechanism
Conclusions
In summary, we have developed a visible light mediated C(sp2)-
C(sp2) cross-coupling reactions employing arylsilanes and
aryldiazonium salts under ternary catalyst system involving
Ph3PAuCl, [Ru(bpy)3(PF6)2] and Cu(MeCN)4BF4. Mechanistically, the
reaction is believed to proceed via the photocatalytic oxidation of
Au(I) to Au(III) followed by successive Si/Cu and Cu/Au(III)
transmetalation as key steps. Though, the multicatalytic systems,
wherein two or more catalysts work simultaneously to form
products are known,22 the use of ternary catalytic system in the
merged gold/photoredox catalysis has not yet been documented.
The finding of the addition of copper salts in Au/Ru photoredox
catalysis should be applicable to broad range of gold-catalyzed
cross-coupling reactions. Further investigations to understand the
reaction mechanism and especially the precise role of copper
catalyst are currently ongoing.
Scheme 3. Scope with counteranions of diazonium salts
To gain further mechanistic insights and gather evidences for
Au(I)/Au(III) catalysis, the reaction was monitored with 31P NMR.17
In the beginning of the reaction, 31P NMR showed a major peak at δ
33.9 ppm (Ph3PAuCl). However, after complete consumption of the
starting material 1a (after 24 h) the peak at δ 33.9 ppm completely
disappeared, while a new peak appeared at δ 22.9 ppm. This peak
could be attributed to the phosphonium salt A [(Ph3P-Ar)+ where Ar
= p-Cl-C6H4], which was further confirmed with HRMS analysis.4,9b
These results suggests the intermediacy of Au(III)-aryl intermediate
and the involvement of Au(I)/Au(III) catalysis at large.
Conflicts of interest
There are no conflicts to declare.
Based on the gathered experimental evidences and literature
known reports, a plausible mechanism for the reaction is depicted
in Scheme 4. At first, irradiation of the photocatalyst [Ru(bpy)3]2+
with visible light would results in the formation of an excited
*[Ru(bpy)3]2+ which gets engaged in single-electron transfer (SET)
with the aryldiazonium salt 2a to give the aryl radical along with the
Acknowledgements
Generous financial support by IISER Bhopal is gratefully
acknowledged. We thank Dr Apurba L. Koner for helping us in
determining quantum yield of the reaction. IC and MOA thanks UGC
and CSIR respectively for the award of Senior Research Fellowship.
oxidized species [Ru(bpy)3]3+ 19
The aryl radical generated from
.
Notes and reference+
photoredox cycle, then adds to the electrophilic Au(I) center I to
give the Au(II) species II.20 Subsequent single electron oxidation of
the resulting aryl gold(II) complex by the [Ru(bpy)3]3+ would lead to
the aryl gold(III) species III with the regeneration of Ru(II). This
intermediate III might undergo transmetalation with the aryl-
copper species; generated in situ by transmetalation of arylsilanes
and Cu(I) catalyst; to generate gold(III) intermediate IV. The
intermediate IV is now set to go for fast reductive elimination21 to
afford the desired cross coupled bi-aryl compounds with the
regeneration of Au(I) catalyst. It should be noted that the radical
1
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