Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear PdI Catalysis

Article abstract of DOI:10.1002/anie.201906063

S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S-aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C?SP(=O)(OR′)(OR′′) coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air- and moisture-stable Pd^I dimer. Our mechanistic and computational data suggest distinct dinuclear Pd^I catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry.

Full text of DOI:10.1002/anie.201906063

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Accepted Article
Title: Arylation of Axially Chiral Phosphorothioate Salts via Dinuclear
Pd(I) Catalysis
Authors: Xiang-Yu Chen, Maoping Pu, Hong-Gang Cheng, Theresa
Sperger, and Franziska Schoenebeck
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201906063
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10.1002/anie.201906063
Angewandte Chemie International Edition
DOI: 10.1002/anie.201((will be filled in by the editorial staff))
Pd(I) dimer catalysis
Arylation of Axially Chiral Phosphorothioate Salts via Dinuclear Pd(I)
Catalysis
Xiang-Yu Chen, Maoping Pu, Hong-Gang Cheng, Theresa Sperger and Franziska Schoenebeck*
Abstract: S-aryl phosphorothioates are privileged motifs in
pharmaceuticals, agrochemicals and catalysts; yet, the challenge
of devising a straightforward synthetic route to enantioenriched
S-aryl phosphorothioates has remained unsolved to date. We
herein demonstrate the first direct C-SP(=O)(OR')(OR'') coupling
of diverse and chiral phosphorothioate salts with aryl iodides,
enabled by an air- and moisture-stable Pd(I) dimer. Our
mechanistic and computational data suggest distinct dinuclear
Pd(I) catalysis to be operative, which allows for operationally
simple couplings with broad scope and full retention of
stereochemistry.
W
hile phosphorothioates display privileged structure/activity
features and find applications as important agrochemicals, top-selling
pharmaceuticals and powerful chiral catalysts (see Scheme 1A), the
control of their inherent chirality remained a daunting synthetic
challenge for decades. Indeed, indirect multistep strategies via P(III)
species have historically been utilized to accomplish this feat,[1] until
Baran’s recent announcement of accessing chiral phosphorothioate
oligonucleotides via an indirect strategy from limonene derived P(V)
reagents under auxiliary control (Scheme 1C).[2] On the other hand,
the synthesis of chiral phosphorothioate salts has been realized
through a straightforward three step sequence.[3] As such, if it were to
be possible to further derivatize these salts at ‘S’ without
compromising on their stereochemical integrity, then access to the
wider phosphorothioate class of compounds would in principle be
unleashed.
In this context, the synthesis of chiral aryl phosphorothioates,
which are commonly found in drugs, pesticides and bioactive
compounds,[4] would require the direct coupling of the salt with a Csp2
center (Scheme 1D). If realizable, this strategy would be highly
powerful, as it would allow for the introduction of the phosphoro-
thioate moiety in any desired chirality and at any stage in a synthesis.
However, although thiolations of Csp2 sites, especially aryl halides,
are well precedented and can be accomplished via Pd(0)-catalyzed
cross coupling reactions,[5] to date, no general, safe, robust and direct
Csp2-SP(=O)(OR2)(OR3) coupling to access aryl phosphorothioates
exists.[6] Instead, the vast majority of synthetic approaches rely on a
bond formation at the phosphorus center directly (i.e. S-P coupling,
Scheme 1B),[7] which has so far not been accomplished in a
stereoselective manner.
Scheme 1. Motivation and synthetic strategy.
Owing to the general mildness and high functional group
tolerance, which are key requirements for late-stage synthetic
applications, a Pd(0)/Pd(II) catalyzed cross-coupling approach appears
ideal at first sight to accomplish this goal. However, when we
subjected various Pd(0) catalysts to iodobenzene and
NMe4[SP(=O)(OPh)2],[8] such as Pd(PPh3)4 or Pd2(dba)3/dppf, no
coupling was observed (see Figure 1A). Moreover, when we
subjected the phosphorothioate salt to a Pd(II) complex and heated the
corresponding mixture, we did not observe the corresponding product
2.[10] Our computational studies support this observation,[9] indicating
that the iodide/phosphorothioate exchange at [LnPd(II)(Ph)(I)],
We therefore set out to develop a method to access diverse and
chiral phosphorothioates in a direct coupling approach with widely
available aryl halides.
1
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10.1002/anie.201906063
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followed by reductive elimination of Ar-SP(=O)(OPh)2 has a
prohibitively high activation free energy barrier of ∆G‡ ≥ 30 kcal/mol
and is endergonic. For comparison, the corresponding thiolation, i.e.
Ar-SPh reductive elimination is characterized by a ~ 10 kcal/mol
lower activation free energy barrier and significantly increased
driving force (see supporting information for details). As such, and in
agreement with the lack of literature precedence, Pd(0)/Pd(II) catalysis
appears to not be an optimal strategy to accomplish C-
SP(=O)(OR2)(OR3) coupling.
Pd(I) dimer, suggesting that the iodine in 1 can be exchanged for a
phosphorothioate.[13]
Table 1: Scope of the Pd(I)-catalyzed phosphorothioation of aryl iodides.[a]
Figure 1. Free energy profile of Pd(I)-catalyzed coupling of PhI with
[SP(O)(OPh)2]−. Gibbs free energies (in kcal/mol) shown, calculated at the SMD
(toluene) M06L/def2TZVP//B3LYP-D3/6-31G(d, p) (SDD for Pd, I) level of theory.
We previously established that dinuclear Pd(I) catalysis is a viable
strategy to circumvent potentially poisonous Pd(II) intermediates as
well as alter the driving force of the transformation.[11] Our extensive
mechanistic studies had indicated that the dimer’s bridging iodines
are initially exchanged by the nucleophilic coupling partner, and the
newly formed Pd(I) complex then reacts with the aryl halide, therefore
formally reversing the sequence of elementary steps (see Figure 1B).
As such, we envisioned that a dinuclear Pd(I) coupling protocol[11,12]
might offer a solution to the phosphorothioate problem.
To assess whether Pd(I)-dimer catalyzed phosphorothioation
would be feasible, we undertook computational studies of the
coupling with iodobenzene, which clearly indicated that there is a
pronounced driving force to convert iodobenzene to the C-
SP(=O)(OPh)2 coupled product (Figure 1). The activation barrier was
found to be in the range of our previous findings of dinuclear Pd(I)
catalysis,[11,12] and as such appeared to be feasible.
A key requirement of the Pd(I) dimer catalysis concept is that the
coupling partner will also function as a stabilizing bridging unit in the
Pd(I) dimer. To examine this, we subjected 4 equiv. of tetramethyl
ammonium phosphorothioate salt to a solution of the air-stable, iodine
bridged Pd(I) dimer 1. To our delight, within 2 h at room temperature
we saw the appearance of a signal at 97.9 ppm upon 31P-NMR
spectroscopic analysis, which is very reminiscent of a functionalized
[a] Yields of isolated products 2-27 after chromatography. [b] The reaction mixture
was stirred for 36 h.
We next set out to explore whether Pd(I) catalyzed
phosphorothioation of aryl iodides is also feasible. To our delight, the
desired O,O-diphenyl phosphorothioate 2[14] was obtained in 83%
yield in the presence of 5 mol% of [PdI(μ-I)(PtBu3)]2 dimer 1 (Table
1). Encouraged by these findings, we subsequently turned to explore
the wider scope of the transformation (Table 1). A series of aryl
iodides bearing electron-donating or electron-withdrawing
substituents (R = 4-Me, 4-nBu, 4-tBu, 4-F, 4-Cl and 4-Ph) reacted
2
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10.1002/anie.201906063
Angewandte Chemie International Edition
smoothly and gave the corresponding products 3–8 in good yields.
The reactions of sterically hindered ortho-substituted (2-MeO, 2-Me
and 2-Ph) aryl iodides also proceeded well, with slightly lower yield
observed with meta substitution (9–12). For 10, prolonging the
reaction time increased the product yield. The reactions of
disubstituted substrates were also successful without any loss of yield
(13 and 14). This was also true for the polyaromatic iodides giving
rise to products 15 and 16. Moreover, the method tolerated a variety
of functional groups, such as esters and morpholines (17–19).
The effect of O,O-dialkyl phosphorothioate salt was examined as well.
Various substituted aryl iodides were readily coupled under the
standard reaction conditions and the corresponding products 20–24
were obtained in excellent yields. Notably, the chirality in the
substituents of the salt was retained (25–27).
C2-symmetric TADDOL-derived phosphorothioate salts with a
variety of aryl iodides, resulting in the desired products 28-39 in very
good yields. The absolute configuration of the product 30 was
determined by X-ray crystallographic analysis (see Table 2),
unambiguously confirming the complete retention of chirality.[16]
In conclusion, while the examined Pd(0)/Pd(II) catalysis failed to
deliver the phosphorothioation of aryl iodides as a consequence of
disfavoured exchange at Pd(II) and a high reductive elimination barrier,
the mechanistically distinct dinuclear Pd(I) catalysis operates with an
orthogonal driving force that allows for the first catalytic S-arylation
of phosphorothioate salts with aryl iodides. The method is
characterized by generality, broad scope and operational simplicity,
making use of an easily accessible phosphorothioate salt and an air-
stable Pd(I) dimer. The stereochemical integrity of chiral salts was not
compromised in the coupling process, allowing the efficient assembly
of axially chiral S-aryl phosphorothioates. In light of the promising
properties of S-aryl phosphorothioate compounds as well as the
privileged Pd(I) catalysis reactivity, we anticipate that the presented
methodology will facilitate numerous applications in the
agrochemical, pharmaceutical and stereoselective synthesis arenas.
Table 2. Applications of the coupling strategy to the efficient synthesis of axially
chiral S-aryl phosphorothioates.[a]
Acknowledgements
We thank the RWTH Aachen and the European Research Council
(ERC-637993) for funding. Calculations were performed with
computing resources granted by JARA-HPC from RWTH Aachen
University under project ‘jara0091’.
Conflict of interest
The authors declare no conflict of interests.
Received: ((will be filled in by the editorial staff))
Published online on ((will be filled in by the editorial staff))
Keywords: dinuclear catalysis • S-aryl phosphorothioate • axial
chirality • computation
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4
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Pd(I) dimer catalysis
X.-Y. Chen, M.-P. Pu, H.-G. Cheng, T.
Sperger, F. Schoenebeck*
Page – Page
Arylation of Axially Chiral
Phosphorothioate Salts via Dinuclear
Pd(I) Catalysis
5
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