Palladium-Catalyzed Asymmetric Allylic Allylation of Racemic Morita–Baylis–Hillman Adducts

Article abstract of DOI:10.1002/anie.201609332

A palladium-catalyzed asymmetric allyl–allyl cross-coupling of acetates of racemic Morita–Baylis–Hillman adducts and allylB(pin) has been developed using a spiroketal-based bis(phosphine) as the chiral ligand, thus affording a series of chiral 1,5-dienes bearing a vinylic ester functionality in good yields, high branched regioselectivities, and uniformly excellent enantioselectivities (95–99 % ee). Further synthetic manipulations of the allylation products provided novel ways for rapid access to a range of chiral polycyclic lactones and polycyclic lactams, as well as the antidepressant drug (?)-Paroxetine, in high optical purities.

Full text of DOI:10.1002/anie.201609332

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201609332
German Edition: DOI: 10.1002/ange.201609332
Asymmetric Catalysis
Palladium-Catalyzed Asymmetric Allylic Allylation of Racemic
Morita–Baylis–Hillman Adducts
Xubin Wang, Xiaoming Wang, Zhaobin Han, Zheng Wang,* and Kuiling Ding*
Abstract: A palladium-catalyzed asymmetric allyl–allyl cross-
coupling of acetates of racemic Morita–Baylis–Hillman
adducts and allylB(pin) has been developed using a spiro-
ketal-based bis(phosphine) as the chiral ligand, thus affording
a series of chiral 1,5-dienes bearing a vinylic ester functionality
in good yields, high branched regioselectivities, and uniformly
excellent enantioselectivities (95–99% ee). Further synthetic
manipulations of the allylation products provided novel ways
for rapid access to a range of chiral polycyclic lactones and
polycyclic lactams, as well as the antidepressant drug (À)-
Paroxetine, in high optical purities.
T
ransition metal catalyzed asymmetric allylic substitution
reactions play an important role in modern organic syn-
functionalized chiral 1,5-dienes turned out to be a versatile
[
1]
thesis. Of great value is the allylic allylation, often through
cross-coupling of an allylmetal reagent and an allyl electro-
phile to give 1,5-dienes which are versatile synthetic inter-
synthetic handle for a number of important transformations.
The study was inspired by our recent disclosure of the
unique bifunctional role of spiroketal-based bis(phosphine)
ligand (SKP) for the control of regioselectivity in palladium-
catalyzed asymmetric allylic aminations of acetates of MBH
[2]
[3]
mediates. A breakthrough in the field of asymmetric allyl–
allyl cross-coupling was made in 2010, when Morken and co-
workers reported the reaction of allylic carbonates with allyl
boronates in the presence of a chiral diphospine/palladium
catalyst, to provide the branched chiral 1,5-dienes with high
regio- and enantioselectivities. Feringa and co-workers later
reported a phosphoramidite/Cu catalyst for asymmetric syn-
thesis of branched chiral 1,5-dienes from allylic bromides and
allyl Grignard reagents. Very recently, Carreira and co-
workers disclosed first examples on the enantioselective
cross-coupling reactions of racemic branched allylic alcohols
with allylsilanes and 1,1-disubstituted terminal alkenes using
an Ir/(P,olefin) complex. Despite the fact that Morita–
Baylis–Hillman (MBH) adducts, a type of functionalized
allylic compounds, have been widely used in numerous
[
11,12]
adducts.
The initial attempts using either allyl stannanes
or allyl silianes to react with the acetates of the MBH adducts
in the presence of a Pd/SKP catalyst system did not afford any
desired allyl–allyl cross-coupling products (see the Support-
ing Information). Gratifyingly, allylic pinacolatoboronate,
[allylB(pin)] (2a), proved to be an effective nucleophile for
allyl–allyl cross-coupling with the MBH adduct acetate 1a
(see Table 1). A preliminary survey of reaction parameters for
SKP/[Pd (dba) ]-catalyzed cross-coupling of 1a and allyl-
[
4]
[
5]
2
3
B(pin) revealed that the reaction was best performed in
dichloromethane at room temperature for 17 hours with CsF
as an additive, thereby affording the branched allylation
product 3a in 92% yield with excellent chemo-, regio-, and
enantioselectivities (B/L = 92:8, 97% ee; see the Supporting
Information). Under the optimized reaction conditions, the
impact of the palladium precursors and chiral ligands on the
outcomes of the cross-coupling were further evaluated and
the results are summarized in Table 1. While the reactivity
and/or the branched/linear regioselectivity (3a/4a) varied
significantly from case to case, excellent ee values (96–97%)
of the branched product 3a were attained using the (S,S,S)-
SKP series of ligands (entries 1–4). In contrast, (R)-furyl-
BIPHEP, which performed well in Morkenꢀs catalyst
[6]
[
7]
synthetic applications, thus far their allyl–allyl cross-cou-
[8]
pling reactions invariably afford achiral linear products, and
the corresponding asymmetric version has not yet been
realized. Herein we report the first example of the enantio-
selective allylic allylation of acetates of MBH adducts using
the palladium complex of a spiroketal-based chiral diphos-
[
9,10]
phine (SKP)
as the catalyst. The resultant densely
[
*] X. Wang, Dr. X. Wang, Dr. Z. Han, Dr. Z. Wang, Prof. Dr. K. Ding
State Key Laboratory of Organometallic Chemistry, Shanghai Insti-
tute of Organic Chemistry, Chinese Academy of Sciences
[4]
system, provided moderate enantioselectivity (60% ee)
albeit with high branched regioselectivity (3a/4a = 92:8;
345 Lingling Road, Shanghai 200032 (China)
E-mail: kding@mail.sioc.ac.cn
[13]
entry 5). Unfortunately, several privileged chiral ligands
Prof. Dr. K. Ding
University of Chinese Academy of Sciences
Beijing 100049 (China)
such as (R)-BINAP, (R)-SDP, and (R,R)-Trost ligand, only
afforded unsatisfactory results (entry 6–8). With (S,S,S)-SKP
as the ligand, use of other palladium salts, for example,
and
3
[
Pd(h -C H )Cl] , Pd(OAc) , or [Pd(CH CN) Cl ], as catalyst
Collaborative Innovation Center of Chemical Science and Engineer-
ing, Tianjin 300071 (China)
3
5
2
2
3
2
2
precursors also delivered excellent results, mostly comparable
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[
a]
Table 1: Catalyst survey for asymmetric allyl–allyl cross-coupling of 1a
with allylB(pin).
Table 2: Substrate scope for the asymmetric allyl–allyl cross-couplings.
[
a]
[
b]
Pd salt (mol%)
[Pd (dba) ] (1)
Ligand
3a/
Yield
[%]
ee
[%]
[
c]
[d]
[e]
4
a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
SKP
92:8
92
13
19
41
76
85
60
12
91
90
94
12
72
61
91
33
97
97
97
96
60
25
15
52
97
96
94
–
2
3
[Pd (dba) ] (1)
o-Tol-SKP
p-Tol-SKP
xyl-SKP
furyl-BIPHEP
BINAP
Trost ligand
SDP
20:80
>20:1
88:12
92:8
2
3
[Pd (dba) ] (1)
2
3
[Pd (dba) ] (1)
2
3
[Pd (dba) ] (1)
2
3
[Pd (dba) ] (1)
92:8
2
3
[Pd (dba) ] (1)
66:34
87:13
92:8
90:10
94:6
79:21
92:8
87:13
92:8
2
3
[Pd (dba) ] (1)
2
3
[{Pd(C H )Cl} ] (1)
SKP
SKP
SKP
SKP
SKP
SKP
SKP
SKP
3
5
2
0
1
2
3
4
5
6
Pd(OAc) (2)
2
[Pd(CH CN) Cl ] (2)
3
2
2
PdCl (2)
2
[Pd (dba) ] (0.5)
97
97
97
97
2
3
[Pd (dba) ] (0.2)
2
3
[{Pd(C H )Cl} ] (0.5)
3
5
2
[{Pd(C H )Cl} ] (0.2)
89:11
3
5
2
[a] Unless otherwise noted, all reactions were performed with 1a
(
0.2 mmol), 2a (0.24 mmol), CsF (1.0 mmol), and the specified catalyst
in CH Cl (2.5 mL) at RT for 17 h. [b] In each case, the ligand loading was
2
2
1
1
.25 molar equiv relative to that of Pd. [c] Determined by H NMR
spectroscopy. [d] Yield of the isolated 3a and 4a. [e] The ee value of 3a
was determined by HPLC on a chiral stationary phase. dba=dibenzy-
lideneacetone.
[
0
[
a] For reaction conditions, see entry 15 in Table 1. Substrate scale of
.4 mmol. The absolute configurations were assigned by CD spectra.
b] [{Pd(C H )Cl} ] (0.008 mmol), and (S,S,S)-SKP (0.02 mmol). [c] 1b
3
5
2
(
0.2 mmol), 2b (0.3 mmol), CsF (2 mmol), [{Pd(C H )Cl} ] (0.01 mmol)
3 5 2
and (S,S,S)-SKP (0.025 mmol) in CH Cl (2.5 mL), 17 h, 408C.
2
2
to those of [Pd (dba) ] (entries 9–11 versus 1), except for the
2
3
case using PdCl (entry 12). Further trials to lower the catalyst
to be more demanding. For the reaction of 1b with 2-methyl-
substituted allyl boronate, methallylB(pin) (2b), higher
2
3
loadings were thus performed using either [{Pd(h -C H )Cl} ]
3
5
2
3
or [Pd (dba) ] along with a SKP ligand as the catalyst, and
loadings of both the catalyst (5 mol% [{Pd(h -C H )Cl} ],
2
3
3
3
5
2
[
{Pd(h -C H )Cl} ] turned out to be superior in this context
12.5 mol% SKP) and the CsF activator (10 molar equiv), as
well as a slightly elevated temperature (408C), were required
for a smooth catalysis, to give the corresponding allylation
product 3n in good yield (83%) with excellent regio- and
enantioselectivity (3n/4n = 77:23, 95% ee).
3
5
2
(
entries 15 and 16 versus 13 and 14).
With the optimized reaction conditions in hand, we
proceeded to examine the reaction scope, and the results
are summarized in Table 2. By using the unsubstituted
allylboronate 2a as the nucleophile, both electron-donating
and electron-withdrawing groups on the phenyl rings of MBH
adducts 1a–m were well tolerated, and the corresponding
cross-coupling products 3a–m were obtained in good yield
with consistently excellent enantioselectivities (95–99% ee).
The branched/linear regioselectivities (3/4) for the allylation
of 1a–l were generally high (> 86:14), with the exception of
A preliminary study on the reaction mechanism was
carried out by varying the structure of substrates, using either
linear or branched, and including enantioenriched allyl
acetates and several isomeric allylic boronates (see
Scheme S2 in the Supporting Information). The observation
of the branched allyl–allyl cross-coupling product being the
major isomer, and essentially identical asymmetric induction
suggests that an inner-sphere 3,3’-reductive elimination might
be operative, analogous to that disclosed by Morken and co-
1
4
m, which afforded more of the linear coupling product (3m/
m = 67:33), probably because of the sterically congested o-
[
4]
tolyl group in 1m. In contrast, the reactivity and selectivity
control in the reactions of substituted allylboronates proved
workers. Considering the known bifunctional role of
spiroketal-based bis(phosphine) (SKP) ligands in the allylic
2
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[
12]
substitution of acetates of MBH adducts, as well as the
outcomes of these reactions (see Scheme S2), the key
intermediates involved in inner-sphere 3,3’-reductive elimi-
established by X-ray diffraction analysis (Scheme 2A).
Extension of the PIFA/Sc(OTf) -mediated oxidative cycliza-
3
tion to the p-toluensulfonyl (Ts) modified amides 7a–c
provided a one-step synthesis of the polycyclic lactams 8a–c
(94–96% ee) under similarly mild reaction conditions (Sche-
me 2A). It is noteworthy that the structures of the polycyclic
[
4,14]
nation
were thus proposed (Scheme 1) to illustrate the
high regio- and stereoselectivity in the present allyl–allyl
cross-coupling.
[
15]
lactams 8a–c incorporate
a
benzomorphan core
(benzobicyclo[3.3.1]) as the scaffold, which has been recog-
nized as the key subunit in a wide range of biologically active
natural products such as morphine, codeine, and pentazoine,
[16]
as well as a variety of artificial analgesics. In addition, the
exocyclic C=C bond in 8a–c might also serve as a handle for
further synthetic manipulations. Thus, this new transforma-
tion provides a simple and useful tool for the efficient
construction of the synthetically challenging chiral polycyclic
structures from open-chain precursors. While the mechanistic
details for the novel oxidative cyclization of either 5a–c or
Scheme 1. Proposed model for inner-sphere 3,3’-reductive elimination
in allyl–allyl cross-coupling.
7
a–c are still unclear at present, a plausible pathway is
The resultant enantioenriched products (3), bearing an
ester group in proximity to the 1,5-diene moiety, proved to be
versatile building blocks for the synthesis of some useful
complex molecules in a number of interesting transforma-
tions. The practical utility of the reaction was first showcased
in the rapid construction of some important chiral polycyclic
lactones and lactams, as shown in Scheme 2. Treatment of 5a–
c, the hydrolytic products of 3a–c, with phenylliodine(III)
bis(trifluoroacetate) (PIFA) and a catalytic amount of Sc-
tentatively proposed in Scheme 2B. PIFA can induce a single-
[17]
electron-transfer (SET) from the electron-rich aryl rings of
5 to produce an arene radical cation of the type A, as has been
demonstrated in the elegant studies by Kita and co-work-
[
18]
ers. Subsequently, the electrophilic radical A may undergo
an intramolecular 5-endo-trig cyclization by addition to the
terminal olefinic carbon atom, to generate the secondary C-
centered radical species B. Further oxidative lactonization
and deprotonation of B gives the carbocation C, which can
rearrange to an arenium ion D by an intramolecular 1,2-alkyl
shift. Further deprotonation of D leads to rearomatization to
afford the polycyclic lactones 6a–c as the final products. The
PIFA-promoted oxidative cyclization of 7a–c to 8a–c seems
likely to follow an analogous mechanism.
(
OTf) at 08C delivered the polycyclic lactones 6a–c in good
3
yields with excellent optical purities (92–96% ee). The
structure of the polycyclic molecule 6a was unambiguously
The synthetic utility of the titled catalysis was further
explored in the formal synthesis of (À)-Paroxetine, a potent
serotonin reuptake inhibitor widely used in the treatment of
[
19]
depression, anxiety, and panic disorders.
The reaction
sequence is shown in Scheme 3, with the fluorine-containing
cross-coupling product (S)-3d as the starting material, which
was readily obtained in high optical purity (95% ee) under
reaction conditions illustrated in Table 2 using (R,R,R)-SKP
as the chiral ligand. The key intermediate, 3-hydroxymethyl 4-
Scheme 2. A) Synthetic utility of the cross-coupling products in the
preparation of the polycyclic lactones 6a-c and polycyclic lactams 8a–
c. Reaction conditions: a) 3a–c, LiOH, THF/H O (1:1), reflux, 24 h; b)
2
5
a–c, PIFA, Sc(OTf) , CH CN, 08C, 12 h; c) 5a–c, p-toluenesulfonyl
Scheme 3. Formal synthesis of (À)-Paroxetine. Reaction conditions:
a) mCPBA (1.5 equiv), CH Cl , 08C–RT, 17 h; b) HIO (1.2 equiv),
3
3
isocyanate (PTSI), Et N, THF, 608C, 3 h; d) 7a–c, PIFA, Sc(OTf) ,
3
3
2
2
5
CH CN, 08C, 12 h. X-ray structure of 6a is shown with thermal
THF/H O (3:1), 08C, 1 h; c) BnNH (3 equiv), NaBH CN (5 equiv),
AcOH (6 equiv), MeOH, RT, 17 h; d) tBuOK (3 equiv), tBuOH
3
2
2
3
[
20]
ellipsoids at 50% probability. B) Proposed mechanism for PIFA-
mediated oxidative cyclizations of 5. PIFA=phenyliodine bis(trifluoro-
acetate), THF=tetrahydrofuran, Ts=4-toluenesulfonyl.
(1.5 equiv), toluene, RT, 1 h; e) LiAlH (10 equiv), THF, 08C, 1 h.
4
mCPBA=m-chloroperbenzoic acid.
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Communications
Chemie
[19e]
arylpiperidine (11), for synthesis of (À)-Paroxetine
can be
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2
readily obtained in a five-step procedure in 36% yield.
In summary, an efficient and mild asymmetric allyl–allyl
cross-coupling reaction of acetates of MBH adducts and
allylboronates has been developed using a SKP/palladium
complex as the catalyst, to afford a range of highly function-
alized chiral 1,5-dienes in good yields, high regioselectivities,
and excellent enantioselectivities (95–99% ee). Synthetic
utilities were demonstrated in a number of simple but
powerful transformations involving the resultant 1,5-dienes,
which provided versatile scaffolds for rapid access to
a number of complex molecules, including some polycyclic
lactones and biologically interesting polycyclic lactams, as
well as the anti-depression drug (À)-Paroxetine.
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Conflict of interest
The authors declare no conflict of interest.
Keywords: allylic compounds · asymmetric catalysis ·
heterocycles · palladium · P ligands
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[
20] CCDC 1423316 (6a) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre.
[
[
Manuscript received: September 23, 2016
Revised: November 12, 2016
Final Article published: && &&, &&&&
6] a) J. Y. Hamilton, N. Hauser, D. Sarlah, E. M. Carreira, Angew.
Chem. Int. Ed. 2014, 53, 10759; Angew. Chem. 2014, 126, 10935;
4
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Asymmetric Catalysis
X. Wang, X. Wang, Z. Han, Z. Wang,*
K. Ding*
&&&& — &&&&
Palladium-Catalyzed Asymmetric Allylic
Allylation of Racemic Morita–Baylis–
Hillman Adducts
SKP off: The asymmetric allyl–allyl cross-
coupling reaction between Morita–
Baylis–Hillman adducts and allylboro-
nates in the presence of a SKP/palladium
complex provided a facile synthesis of
optically active 1,5-dienes. The products
can be readily transformed into a range of
chiral polycyclic lactones and lactams, as
well as the antidepressant drug (À)-
Paroxetine, in high optical purities.
Angew. Chem. Int. Ed. 2016, 55, 1 – 5
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!