Gold-Catalyzed 1,2-Diarylation of Alkenes

Article abstract of DOI:10.1002/anie.202002141

Herein, we disclose the gold-catalyzed 1,2-diarylation of alkenes through the interplay of ligand-enabled Au^I/Au^III catalysis with the idiosyncratic π-activation mode of gold complexes. Unlike the classical migratory-insertion-based approach to 1,2-diarylation, the present approach not only circumvents the formation of direct Ar?Ar′ coupling and Heck-type side products but more intriguingly demonstrates reactivity and selectivity complementary to those of previously known metal catalysis (Pd, Ni, or Cu). Detailed investigations to underpin the mechanistic scenario revealed oxidative addition of aryl iodides to an Au^I complex to be the rate-limiting step owing to the non-innocent nature of the aryl alkene.

Full text of DOI:10.1002/anie.202002141

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Accepted Article
Title: Gold-Catalyzed 1,2-Diarylation of Alkenes
Authors: Nitin T. Patil, Chetan C. Chintawar, and Amit K. Yadav
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202002141
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10.1002/anie.202002141
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Gold-Catalyzed 1,2-Diarylation of Alkenes
Chetan C. Chintawar, Amit K. Yadav and Nitin T. Patil*
Abstract: Herein, we disclose the first gold-catalyzed 1,2-diarylation
of alkenes by adopting the interplay of ligand-enabled Au(I)/Au(III)
catalysis with idiosyncratic -activation mode of gold complexes.
Unlike the classical migratory insertion based approach to 1,2-
diarylation, the present approach not only circumvents the formation
of direct ArArꞌ coupling and Heck-type side products but more
intriguingly furnishes reactivities and selectivities complementary to
that of previously known metal catalysis (Pd, Ni or Cu). Detailed
investigation was carried out to underpin the mechanistic scenario;
which revealed oxidative addition of aryl iodides to Au(I) complex to
be the rate limiting step owing to non-innocent nature of aryl alkene.
Over the decades, transition metal-catalyzed 1,2-
difunctionalization of CC multiple bonds has evolved as a
celebrated chemical transformation owing to its inherent ability
to streamline the construction of complex molecular scaffolds.[1]
One of the most crucial transformations of this class is the 1,2-
diarylation of alkenes and Pd, Ni, and Cu complexes have
emerged as key players to catalyse these processes. In general,
three strategic approaches to achieve 1,2-diarylation of alkenes
have been developed (Scheme 1a) which include: (1) oxidative
1,2-diarylation of alkenes leading to the installation of two
identical aryl groups using a sole organometallic reagent
(ArY),[ 2 ] (2) reductive diarylation of alkenes leading to the
installation of two aryl electrophiles (ArX),[3] (3) cross-coupling
mode for diarylation of alkenes which introduce aryl groups by
utilizing an aryl electrophile (ArX) and aryl nucleophile (ArꞌYꞌ
or ArꞌH) under Pd,[4] Ni,[5] Cu[6] catalysis. Although generality of
these 1,2-diarylations is well established, most of these
transformations utilize prefunctionalized starting materials and
primarily rely on the classical migratory insertion pathways
furnishing more or less similar reactivity and selectivity pattern.
Scheme 1. Background and synopsis of present work.
Additionally, almost in all cases highly facile direct ArArꞌ
coupling and conventional Heck-type reaction poses
a
Bourrissou and co-workers demonstrated that such arduous
step can be facilitated by utilizing hemilabile (P,N)-ligands.[13]
Reviving the cross-coupling reactivity mode in gold catalysis,
ligand-enabled Au(I)/Au(III) catalysis have lately allowed the
development of redox neutral CC, CN and CS cross-coupling
reactions using aryl halides as feedstock.[ 14 ] However, we
believe that the real potential of gold catalysis could be best
harnessed if this newly established ligand-enabled cross-
coupling reactivity is integrated with the unique -activation
chemistry. Through engineering these two reactivity modes, we
sought to develop a mechanistic paradigm by which non-
prefunctionalized substrates such as aryl alkenes 1 can be
efficiently transformed to 1,2-diarylated products 3 using aryl
halides 2 as coupling partner (Scheme 1b). We envisioned that
the active Au(I) catalyst bearing hemilabile (P,N)-ligand would
undergo oxidative addition with ArꞌX 2 to generate the Au(III)-
aryl complex A which after halide abstraction would selectively
intercept with aryl alkene 1 to generate Au(III)--complex B.
Given that the Au(III)-complexes are known to strongly activate
CC multiple bonds, we envisaged that the complex B would
effectively undergo carboauration by the nucleophilic attack of
ArH onto activated alkene to form the Au(III)-aryl alkyl
intermediate C. As gold complexes are reluctant to undergo -
hydride elimination,[15] reductive elimination of Au(III)-aryl alkyl
formidable challenge and demands specially designed
substrates or catalysts to suppress these undesired pathways.
Gold catalysts have emerged as inimitable -Lewis acids for
selective functionalizations of CC multiple bonds.[7] However,
owing to the high redox potential of Au(I)/Au(III) couple (E0
=
+1.41 V), gold catalysts do not easily follow two electron redox
cycles[8] as a result a customary practice[9] of using either strong
oxidants[10] or photocatalysts[11] became inevitable requirement
to achieve 1,2-difunctionalization of CC multiple bonds. Despite
the modest efficacy, these strategies could not become
sustainable due to the use of stoichiometric amount of sacrificial
oxidants or highly reactive aryl diazonium salts. Recently
therefore considerable efforts have been devoted to realize the
key oxidative addition of organohalides to Au(I) complexes.[12]
[*]
C. C. Chintawar, A. K. Yadav, N. T. Patil*
Department of Chemistry, Indian Institute of Science Education and
Research Bhopal, Bhauri, Bhopal, 462 066 (India)
E-mail: npatil@iiserb.ac.in
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.202002141
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intermediate C should selectively deliver the desired 1,2-
diarylated product 3. The successful realization of the concept
would open up a “-activation” based approach rather than a
classical “migratory insertion” pathway as prevalent in
aforementioned transition metal catalysis. Herein, we disclose
the successful implementation of our hypothesis along with key
mechanistic insights for accessing two-component 1,2-
diarylation of alkenes.
We initiated our study with a series of stoichiometric
experiments to validate the elementary steps in the proposed
catalytic cycle (Scheme 2). At first, we prepared Au(III)-aryl
complex A by the reaction of (Me-DalPhos)AuCl and 4-
iodoanisole (2a).[16] This complex was then treated in situ with
aryl alkene 1a and AgSbF6 at 78 C. When the reaction mixture
was gently warmed to room temperature and allowed to stir, a
gradual increase in the formation of a non-polar compound was
observed on TLC along with decrease in the Au(III)-aryl complex
A (as confirmed by 31P NMR). Of note, by heating the reaction
mixture to 60 C, a quantitative conversion was witnessed within
30 min. To our delight, isolation and characterization of the
observed compound confirmed the desired diarylation product
3a (63% yield).
requirement of an ethereal linkage. Aryl alkenes (1ab) linked
through NTs group also reacted well; however, the substrates
with relatively labile NAc (1ac) and NBoc (1ad) groups were
found to be not viable. Heteroaryl alkenes such as oxindole,
indole, benzofuran and carbazole derivatives worked well to
furnish 3ai – 3al in good yields (57% – 77%); however, the
corresponding pyridine derivative (1am) succumbed to
quenching of the active catalyst by strong coordination with
pyridine nitrogen.
Table 1. Scope of aryl alkenes[a]
Scheme 2. Stoichiometric experiment.
With this encouraging observation, we next began to
investigate the catalytic variant of the gold-catalyzed 1,2-
diarylation of alkenes.[16] We elected to use aryl alkene 1a, 4-
iodoanisole (2a), (Me-DalPhos)AuCl (5 mol%) and AgSbF6 (1.05
equiv) in 1,2-dichloroethane (DCE) (0.1 M) and allowed to stir at
70 C. Pleasingly, the desired diarylation product 3a was
obtained in 78% yield in just two hours. Notably, addition of 0.5
equiv of base (K3PO4) boosted the yield to 96%. The analysis of
steric and electronic nature of DalPhos ligand suggested that
sterically demanding and electronically rich adamantyl (−Ad) and
hemilabile −NMe2 groups are essential requirements for highly
effective transformation.
[a] Reaction conditions: 0.22 mmol 1, 0.2 mmol 2a, 5 mol% (Me-DalPhos)AuCl,
1.05 equiv AgSbF6, 0.5 equiv K3PO4, DCE (0.1 M), 70 C, 24 h. [b]
Deprotection of protecting group was observed. [c] Starting material 1am
remain unreacted.
Having identified optimal reaction conditions, scope of the
present transformation was investigated by reacting a diverse
range of aryl alkenes 1 with 4-iodoanisole (2a) (Table 1). Of note,
in none of the cases did we observe direct ArArꞌ coupling or
Gratifyingly, diversely substituted aryl iodides 2 reacted
efficiently producing the desired products (4b – 4v) in good to
excellent yields (50% – 93%) (Table 2). In general, electron
deficient aryl iodides were found to furnish slightly attenuated
yields probably because of the difficulty in achieving the key
oxidative addition step.[12h,13] Heteroaryl iodides involving
xanthone (2z) and indole (2ac and 2ad) derivatives were also
competent substrates to furnish respective products in good
yields (60% – 76%). Furthermore, to assess the compatibility of
established protocol within the context of late-stage
functionalization, iodo- derivatives of L-menthol (2ae) and
estrone (2af) were successfully evaluated to afford 4ae and 4af
in 62% and 83% yields, respectively.
Heck-type
side
products
demonstrating
the
high
chemoselectivity of gold-complexes for 1,2-diarylation reactions.
Aryl alkenes bearing different substituents at ortho-, meta- and
para- positions worked well affording 3a – 3v in good to
excellent yields (45% – 99%). Especially, complementary to the
reported 1,2-diarylation methods,[36] present methodology
permits the aryl alkenes bearing OTf or Br substituents at
ortho- position (1q and 1v) to selectively undergo 1,2-diarylation
furnishing the desired products 3q and 3v with excellent yields
(76% and 90%). Furthermore, aryl alkene 1aa also afforded the
desired product in excellent yield (3aa, 86%) opposing the
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Table 2. Scope of aryl iodides[a]
Accordingly, iodoaryl alkene 7 was treated with electron-rich
aromatics such as indole under the standard reaction conditions.
To our delight, the anticipated product 9a was obtained; albeit, in
low yield (42%). However, N-methyl indole worked remarkably
well producing 9b – 9e in good to excellent yields (60% – 98%).
In addition, the synthetically challenging higher membered rings
were also obtained with excellent selectivity (9f and 9g)
featuring the proficiency of the present methodology. To the best
of our knowledge, such reversal of selectivity is completely novel
and not observed before with any other metal catalysts.
Table 4. Scope of iodoaryl alkenes[a]
[a] Reaction conditions: 0.2 mmol 7, 0.22 mmol ArH,
5 mol% (Me-
DalPhos)AuCl, 1.05 equiv AgSbF6, 0.5 equiv K3PO4, DCE (0.1 M), 70 C, 24
h.
[a] Reaction conditions: 0.22 mmol 1a, 0.2 mmol 2, 5 mol% (Me-DalPhos)AuCl,
1.05 equiv AgSbF6, 0.5 equiv K3PO4, DCE (0.1 M), 70 C, 24 h.
Next, a series of experiments were designed to gain
mechanistic insights (Scheme 3). Our initial control experiments
suggested that stoichiometric amount of halide scavenger
(AgSbF6) is essential to (re)generate the active cationic Au(III)
species from Au(III)-aryl complex A (Scheme 3a). Notably,
cationic Au(I) complex cannot catalyze the cyclization of aryl
alkene 1a as hydroarylation product 10 was not observed under
given conditions, suggesting that the highly electrophilic cationic
Au(III) complex is crucial for effective alkene activation. Not
surprisingly, performing both the reactions only with AgSbF6
leaves the starting materials unreacted (Scheme 3a, condition b).
It is worth mentioning that (P,P)- and (P,N)-ligated Au(I)
complexes are known to activate alkenes to form tricoodinated
η2 -complexes owing to the strong back-donation from Au(I)
center.[17 ] This prompted us to investigate whether the aryl
alkenes 1 are really innocent during the catalytic cycle prior to
oxidative addition step. Thus, we chose to monitor the oxidative
addition of (Me-DalPhos)AuCl with 4-iodoanisole (2a) in
presence of aryl alkene 1a via detecting the formation of Au(III)-
aryl complex A with 31P NMR spectroscopy (Scheme 3b).
Notably, the peak resembling to Au(III)-aryl complex A (at 74
ppm) appeared only after 1 h; while, it took about 6 h to
complete the oxidative addition step at room temperature. Even
Interestingly, scope of the present transformation could be
further extended to access 9,10-dihydrophenanthrenes (6a and
6b) by the reaction of 2-allyl-1,1'-biphenyl (5) with aryl iodides
(2r and 2s) (Table 3).
Table 3. Synthesis of 9,10-dihydrophenanthrenes[a]
[a] Reaction conditions: 0.22 mmol 5, 0.2 mmol 2, 5 mol% (Me-DalPhos)AuCl,
1.05 equiv AgSbF6, 0.5 equiv K3PO4, DCE (0.1 M), 70 C, 24 h.
The reaction of haloaryl alkenes of type 7 with an aryl
coupling partner is one of the archetype examples among the
known diarylation methods which yields product of type 8 owing
to the dominant 1,2-migratory insertion chemistry of Pd, Ni or Cu
catalysts (Table 4, path a).[3a,4a,4g,6b] We wondered whether the
present -activation approach would furnish the complementary
reactivity delivering the product 9 owing to the dominant -
activation chemistry of gold catalysts (Table 4, path b).

at 60 C, the oxidative addition step required about 20 min to
complete; whereas, in absence of aryl alkene 1a, the process is
instantaneous at room temperature.[13] All these observations
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766.3471 corresponding to the Au(I)-alkene -complex D was
observed which was further corroborated by tandem mass
spectrometry (MS/MS) analysis. This observation led us to
propose the formation of Au(I)-alkene complex D during the
catalytic cycle. The slow dissociation of alkene would then
generate the active cationic (Me-DalPhos)Au(I) complex which
could undergo oxidative addition with aryl iodide; thus, rendering
it to be the rate limiting step. Next, when terminally deuterated
aryl alkene (E)-1a-D was treated with 4-iodoanisole under the
standard reaction conditions, the corresponding diarylation
product 3a-D was obtained, strongly advocating the anti addition
of aryl groups across CC double bond (Scheme 3c). This
supports the proposed aromatic electrophilic substitution (SEAr)
type mechanism to be operational for carboauration of alkenes.
This was further validated by kinetic isotope effect (KIE) studies
which asserted the values of KH/KD = ~1 and ~1.1 for
competition and parallel experiments, respectively (Scheme 3d).
Furthermore, the putative Au(III)-aryl alkyl intermediate C could
also be detected through mass spectrometry (m/z = 872.3883)
as the MS/MS analysis of the isolated intermediate furnished the
peaks at m/z = 618.2579, 636.2697 and 659.2848 which could
be assigned to the fragments a, b and c respectively (Scheme
3e). (For detailed mechanistic proposal; see ESI, Scheme 6.6).
In conclusion, we have developed the first gold-catalyzed
1,2-diarylation of alkenes by designing a mechanistic paradigm
that showcases the productive integration of ligand-enabled
Au(I)/Au(III) catalysis with intrinsic -activation ability of gold
complexes. The present -activation approach to 1,2-diarylation
not only furnishes the complementary reactivities and
selectivities but also circumvents the direct ArArꞌ coupling and
Heck-type side products commonly observed under Pd, Ni or Cu
catalysis. Moreover, the reaction was found to be highly general
and utilizes non-prefunctionalized substrates to deliver products
in good to excellent yields. Preliminary mechanistic studies
revealed the non-innocent nature of alkene prior to oxidative
addition of Au(I) complex to aryl iodide, rendering it to be a rate
limiting step. These foundations should serve as a strong
platform for further development of various fundamentally novel
1,2-difunctionalizations of C-C multiple bonds. Furthermore,
given the appealing structural features of active Au(III)-
complex[ 18 ] generated during catalytic cycle, the developed
chemistry has potential to offer the most coveted, yet unknown,
asymmetric version of gold-catalyzed 1,2-difunctionalization
reactions.
Acknowledgements
Generous financial support by the Science and Engineering
Research Board (SERB), New Delhi (File No. EMR/2016/
007177 and DIA/2018/000016) is gratefully acknowledged.
C.C.C. and A.K.Y. thanks UGC and IISER Bhopal; respectively,
for fellowships.
Scheme 3. Mechanistic investigations.
indicate a strong interaction existing between aryl alkene and
cationic Au(I) species. Therefore, we postulated that the peak
appearing at 58 ppm might correspond to Au(I)-alkene complex
D.[17] Although all our attempts to isolate the complex D failed; its
formation was detected by monitoring the reaction through mass
spectrometry.[16] The strong peak in mass spectrum at m/z =
Keywords: alkene · 1,2-difunctionalization · -activation · cross-
coupling · gold catalysis
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This article is protected by copyright. All rights reserved.

10.1002/anie.202002141
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Chetan C. Chintawar, Amit K. Yadav
and Nitin T. Patil*
Page No.0000 – Page No.0000
Gold-Catalyzed 1,2-Diarylation of
Alkenes
Disclosed herein is the first gold-catalyzed 1,2-diarylation of alkenes by designing a
mechanistic paradigm that showcases the productive integration of ligand-enabled
Au(I)/Au(III) catalysis with intrinsic -activation ability of gold complexes.
This article is protected by copyright. All rights reserved.