COMMUNICATIONS
DOI: 10.1002/adsc.202100293
Palladium-Catalyzed Alkene Thioacylation: A CÀ S Bond
Activation Approach for Accessing Indanone Derivatives
Jianing Wu,a Wen-Hua Xu,a,* Hong Lu,a,* and Peng-Fei Xub,*
a
Key Laboratory of Synthetic and
Natural Functional Molecule Chemistry of the Ministry of Education,
College of Chemistry & Materials Science,
Northwest University, Xi’an 710069
E-mail: xuwenhua.qf@gmail.com; luh@nwu.edu.cn
State Key Laboratory of Applied Organic Chemistry,
b
College of Chemistry and Chemical Engineering,
Lanzhou University, Lanzhou 730000
E-mail: xupf@lzu.edu.cn
Manuscript received: March 6, 2021; Revised manuscript received: April 11, 2021;
Version of record online: ■■■, ■■■■
can be synthesized using various methods based on
acylation chemistry or metal-catalyzed transforma-
tions. The decarbonylative addition of thioesters to
unsaturated bonds represents an attractive approach for
Abstract: A palladium-catalyzed intramolecular al-
kene thioacylation reaction initiated by the activa-
tion of thioester C(acyl)À S bonds is reported. This
approach successfully suppressed decarbonylation
the simultaneous introduction of carbon and sulfur
and β-hydrogen elimination with related acyl and
functional groups,[7] demonstrated in the pioneering
alkyl metal thiolate intermediates, providing an
works of Pt-catalyzed carbothiolation of alkynes,[8a] as
efficient and atom-economical method to access
well as the recent work of Matsubara et al. on Ni-
indanone scaffolds. Mechanistic studies provide
catalyzed reactions.[8b–d] In contrast, transition-metal-
support for C(acyl)À Pd bond insertion of olefins.
catalyzed thioacylation of unsaturated systems, espe-
The synthetic utility of this protocol is demonstrated
cially for alkene, is relatively underdeveloped
by the further conversion of the newly formed
(Scheme 1A).[9–11] The hitherto known successful ex-
methylene sulfide substituent.
amples are limited to the use of activated olefins such
as allenes[9c] and norbornenes.[9e]
Motivated by the pivotal role of CÀ S bond
formation in organic synthesis and the pharmaceutical
importance of sulfur-containing compounds,[12] we
wanted to explore the feasibility of using a “cut and
sew” approach by investigating thioesters. The intra-
Keywords: Thioacylation; Thioester; CÀ S Bond
activation; Palladium catalysis; Indanone
The transition-metal-catalyzed “cut and sew” trans- molecular insertion of olefins into the C(acyl)À S bonds
formation has recently emerged as a useful strategy for of thioesters, which proceed much faster than inter-
preparing complex molecular structures.[1] This strat- molecular reactions and are easier to control in
egy provides efficient access to substituted molecules transition-metal-catalyzed reaction, leads to an inda-
from readily available alkenes by installing functional none framework, which is a key motif in a number of
groups across their carbonÀ carbon double bonds. biologically important natural products (Figure 1).[13]
Molecular complexity can be built by coupling olefins However, achieving the desired CÀ S bond formation is
with a range of simple, readily available starting not trivial (Scheme 1B, Path A) because decarbon-
materials, such as aldehydes,[2] ketones,[3] esters,[4] and ylative products are generally dominant when olefin
amides.[5]
insertion is slow (Scheme 1B, Path B),[14] and alkyl
Thioesters are more reactive than alcohol-derived metal thiolate intermediates tend to undergo β-hydride
esters because of the poorer orbital overlap between elimination rather than the desired CÀ S bond formation
the sulfur atom and the carbonyl group. They have (Scheme 1B, Path C).[15] Herein, we describe the
similar reactivity to acyl chloride, but they are bench development of a palladium-catalyzed olefin thioacyla-
stable and can be stored for a long time.[6] Thioesters tion reaction of thioesters for rapid access to indanone.
Adv. Synth. Catal. 2021, 363, 1–6
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