Palladium-Catalyzed Asymmetric Construction of Vicinal Tertiary and All-Carbon Quaternary Stereocenters by Allylation of β-Ketocarbonyls with Morita–Baylis–Hillman Adducts

Article abstract of DOI:10.1002/anie.201701455

Palladium-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of β-ketocarbonyls with Morita–Baylis–Hillman adducts has been developed using a spiroketal-based diphosphine (SKP) as the ligand, thus affording a range of densely functionalized products bearing vicinal tertiary and all-carbon quaternary stereodyad in high selectivities. The utility of the protocol was demonstrated by the facile synthesis of some complex molecules by simple product transformations.

Full text of DOI:10.1002/anie.201701455

Angewandte
Communications
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International Edition: DOI: 10.1002/anie.201701455
German Edition: DOI: 10.1002/ange.201701455
Allylic Compounds
Palladium-Catalyzed Asymmetric Construction of Vicinal Tertiary and
All-Carbon Quaternary Stereocenters by Allylation of b-Ketocarbonyls
with Morita–Baylis–Hillman Adducts
Jiawang Liu, Zhaobin Han, Xiaoming Wang, Fanye Meng, Zheng Wang,* and Kuiling Ding*
Abstract: Palladium-catalyzed regio-, diastereo-, and enantio-
selective allylic alkylation of b-ketocarbonyls with Morita–
Baylis–Hillman adducts has been developed using a spiroke-
tal-based diphosphine (SKP) as the ligand, thus affording
a range of densely functionalized products bearing vicinal
tertiary and all-carbon quaternary stereodyad in high selectiv-
ities. The utility of the protocol was demonstrated by the facile
synthesis of some complex molecules by simple product
transformations.
A
lthough substantial progress has been made in the syn-
thesis of singular all-carbon quaternary stereocenters,[1]
catalytic construction of contiguous stereodyads proves far
more difficult because of the increased steric demands and the
Scheme 1. Palladium-catalyzed AAA reactions for the construction of
a) singular all-carbon quaternary stereocenters and b) vicinal stereo-
dyads. EWG=electron-withdrawing group.
stereochemical control in the C C bond formation.[2] Among
the limited methods for building such a motif, some recent
developments involve the use of transition-metal-catalyzed
asymmetric allylic alkylations (AAA)[3] as a versatile tool for
À
Herein, we report the first palladium-catalyzed AAA of b-
ketocarbonyl compounds, both cyclic and acyclic, with
modified MBH adducts.[8,9] With a spiroketal-based diphos-
phine (SKP)[10] as the chiral ligand, a wide range of densely
functionalized products, bearing congested vicinal tertiary
and all-carbon quaternary stereodyads, were obtained with
high branched regioselectivities, and good to excellent
diastereo- and enantioselectivities (Scheme 1b).
À
this challenging C C bond formation. In this context, several
chiral transition-metal catalysts, largely based on either Ir[4] or
Mo,[5] have recently been demonstrated as effective for the
construction of vicinal stereodyads by stereoselective reac-
tions of a prochiral nucleophile with a prochiral allyl electro-
phile. Despite that palladium-catalyzed AAA has been
utilized in the synthesis of singular all-carbon quaternary
stereocenters, for example, by alkylation of a prochiral
enolate with an allylic electrophile (Scheme 1a),[6] however,
to our knowledge only a few examples have been documented
on their use in the construction of such vicinal stereodyads
bearing a quaternary carbon center.[6b] This deficit, presum-
ably owing to the generally preferential formation of the
linear product in palladium-catalyzed allylation, constitutes
a major limitation in palladium-catalyzed AAA reactions.[7]
The research was inspired by the unique behavior of SKPs
in palladium-catalyzed asymmetric allylic aminations of
MBH adducts, wherein the ligand plays a bifunctional role
and allows excellent control over both the branched regio-
and enantioselectivities.[11] We envisioned that SKP/Pd-cata-
lyzed AAA of MBH adducts with nucleophiles of b-ketocar-
bonyl compounds[12] might provide an excellent approach for
the construction of vicinal chiral tertiary and quaternary
centers. Accordingly, the reaction of the MBH adduct 1a and
b-ketoester 2a was taken for a proof-of-concept prototype to
survey the reaction conditions (Table 1). A preliminary
investigation (for details, see the Supporting Information)
revealed that the reaction proceeds smoothly in the presence
of [Pd2(dba)3]/(S,S,S)-SKP (L1) in CH2Cl2 at À208C, thus
affording 3aa in 90% yield with a high branched/linear
selectivity (b/l = 91:9), good diastereoselectivity (12:1 d.r.),
and nearly perfect enantioselectivity (> 99% ee; entry 1). The
diastereoselectivity was further improved to 17:1 and 16:1
(d.r.) by adding a 2.5 volume % of EtOH and H2O,
respectively, to the reaction system without any loss of
regio- or enantioselectivity (entries 2 and 3; hereafter des-
ignated as reaction conditions A and B, respectively). Sub-
sequently, a SKP ligand series (L1–L6) and several privileged
chiral ligands[13] [(R)-BINAP (L7), (R)-SegPhos (L8), (R)-
SDP (L9), and (R,R)-Trost ligand (L10)] were screened in the
[*] Dr. J. Liu, Dr. Z. Han, Dr. X. Wang, F. Meng, Dr. Z. Wang,
Prof. Dr. K. Ding
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
345 Lingling Road, Shanghai 200032 (China)
E-mail: kding@mail.sioc.ac.cn
Dr. J. Liu, F. Meng, Prof. Dr. K. Ding
University of Chinese Academy of Sciences
Beijing 100049 (China)
Prof. Dr. K. Ding
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin 300071 (China)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201701455.
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Table 1: Optimization of the reaction conditions.[a]
Table 2: Substrate scope with respect to the MBH adducts.[a]
Entry
L
Add.[b]
3aa/4aa[c]
d.r.[c]
Yield [%][d]
ee [%][e]
1
2
3
4
5
6
7
8
L1
L1
L1
L2
L3
L4
L5
L6
L7
L8
L9
L10
none
EtOH
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
91:9
91:9
93:7
94:6
90:10
12:1
17:1
16:1
20:1
10:1
90
90
93
87
75
0
72
58
n.o.
n.o.
n.o.
n.o.
>99
>99
>99
98
>99
–
90:10
82:18
–
–
–
–
14:1
4:1
–
–
–
>99
97
9[f]
10[f]
11[g]
12[f]
–
–
–
–
–
[a] Unless otherwise noted, all reactions were performed in CH2Cl2
(2.0 mL) at À208C for 12 h, in the presence of 1a (0.2 mmol), 2a
(0.22 mmol), [Pd2(dba)3] (0.002 mmol), the ligand (L; 0.005 mmol), and
solid LiOH (0.6 mmol). [b] Add. =additive, EtOH or H2O as the additive
(50 mL). [c] The values of 3aa/4aa (b/l) and diastereomeric ratios (d.r.)
of 3aa were determined by 1H NMR analysis. [d] Yield of isolated 3aa.
[e] The ee values of 3aa were determined by HPLC analysis on a chiral
column. [f] 1a was fully recovered after the reaction. [g] About 30% of 1a
was isomerized during the reaction. dba=dibenzylideneacetone,
n.o.=not observed.
[a] Unless otherwise noted, the reactions were performed under
condition A. The data within parentheses are the yields of isolated 3. The
b/l ratios (3:4), d.r. and ee values of 3 were determined following the
methods shown in footnotes of Table 1. The structure of 3ja was
unambiguously established by X-ray diffraction, while the absolute
configurations of the other products were assigned by comparing the
Cotton effect of their CD spectra with that of 3ja. [b] Conditions B.
[c] À258C, 24 h. [d] 18 h. [e] 24 h.
reaction with H2O as the additive. Except for L4, all SKP
ligands furnished the branched product 3aa in good yields
(58–93%) with high branched regioselectivity (b/l = 82:18–
94:6) and excellent ee values (97– > 99% ee), albeit with
d.r. values which varied (entries 3–8). Intriguingly, none of the
well-established chiral diphosphine ligands, L7–L10, deliv-
ered 3aa. Such a sharp contrast in reactivity profile between
SKPs and L7–L10 probably reflects a fundamental difference
in the substrate activation using the corresponding palladium
complexes, hence attesting to the unique role and the superior
performance of SKP ligands in this reaction.
With the optimized reaction conditions in hand, we
proceeded to explore the substrate scope with regard to
racemic MBH adducts using 2a as the nucleophile (Table 2).
In most cases, the reactions were conducted under reaction
conditions A. As shown in Table 2, a wide range of functional
groups on the phenyl rings of MBH adducts (1a–o), either
electron-donating (MeO, Me, BnO) or electron-withdrawing
(Br, Cl, F, CF3, CN), were well tolerated in the reaction, to
give a wide range of densely functionalized products (3aa–
oa). They contained well-defined contiguous stereodyads
bearing an all-carbon quaternary center adjacent to a tertiary
chiral carbon, and were delivered in good to excellent yields
(61–93%) with high branched regioselectivities (b/l = 80:20 to
95:5), good diastereoselectivities (6.4:1 to > 20:1), and
excellent enantioselectivities (92 to > 99% ee). The MBH
substrates with haloaryl moieties, which might be sensitive to
palladium catalysis, also worked well, without adverse effect
on the reaction (3ea, 3ga, 3ia, 3ja). It is interesting to note
that the ester moiety on the MBH adduct exhibited a signifi-
cant effect on the catalysis (especially the enantioselectivity),
as shifting from 1a (ethyl ester) to 1m (methyl ester) resulted
in a decline of the ee value from greater than 99% to 92%
(3aa versus 3ma).
The scope, with respect to prochiral nucleophiles reacting
with 1a, was then explored in the catalysis. As shown in
2
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Table 3: Substrate scope with respect to b-ketocarbonyl nucleophiles.[a]
reactions of a-carboxyethyl tetralone (2h), a-carboxyethyl
indanone (2i), and a-carboxyethyl chroman-4-one (2j)
afforded the corresponding products 3ah–aj with high yields
and excellent ee values, though in some cases a modest
regioselectivity (3ai) and diastereoselectivity (3ai, 3aj) were
obtained. The reactions of the challenging acyclic b-ketoest-
ers 2k and 2l also proceeded smoothly to give the branched
products 3ak and 3al, respectively, with high b/l ratios and
excellent ee values, albeit in a moderate diastereoselectivity.
The reaction of enolate of malonate (2m), generated in situ
with aqueous K2CO3 (3 equiv), gave the allylation product
3am with an excellent b/l ratio and 96% ee. In addition to the
b-ketoesters, b-diketones (2n, 2o) also proved to be viable
substrates for the reaction, thus affording the desired
products 3an and 3ao in good yields with high d.r. values
and greater than 99% ee, though with moderate b/l ratios. The
reaction involving a-cyanocyclopentone (2p) provided the
corresponding product 3ap with high branched regioselectiv-
ity and good ee values, albeit with a modest d.r. value. Finally,
under reaction conditions B 3aa and 3ah were readily
synthesized on gram-scale with extremely high optical
purities (> 99% ee; see the Supporting Information), thus
attesting to the practicality of the protocol.
The synthetic utility of the method was demonstrated in
a number of transformations on the highly functionalized
allylation product 3aa (Scheme 2). Pd/C-catalyzed hydro-
[a] Unless otherwise noted, the reactions were performed under
conditions B. The data within parentheses are the yields of isolated 3. In
each case, the b/l and d.r. values were determined by 1H NMR analysis,
and the ee values for 3 was determined by HPLC using a chiral column.
[b] À258C, 24 h. [c] Yield of isolated 3 and 4. [d] Conditions A. [e] Data
within parentheses are ee values for the minor diastereomer. [f] RT, 12 h,
aqueous K2CO3 (1.0m, 3.0 equiv) as the base.
Scheme 2. Synthetic transformations of the allylation product 3aa.
a) Pd/C, H2, EtOH, RT, 24 h. b) PhNHNH2, TFA, DCE, 508C, 72 h.
c) 1.) NaBH4, MeOH, À658C, 6 h; 2.) aq. HCl, RT, 2 h. d) 1.) NMO,
OsO4, acetone/H2O (9:1), RT,12 h; 2.) Na2S2O3, HCl, RT, 6 h. Thermal
ellipsoids shown at 30% probability. DCE=1,2-dichloroethane,
NMO=N-methyl morpholine N-oxide, TFA=trifluoroacetic acid.
Table 3, a large variety of b-ketocarbonyl compounds, includ-
ing cyclic and acyclic b-ketoesters (2a–l), dimethyl malonate
(2m), b-diketones (2n, 2o), and a-cyanoketone (2p) were
found to be compatible with the procedure (conditions B),
thus affording the corresponding products 3aa–ap in good to
high yields (62–99%). Except for 3ap, all the products (3aa–
ao) were obtained in excellent enantioselectivities (93–
> 99% ee). In contrast, the regio- and diastereoselectivities
of 3aa–ap were found to vary significantly (b/l = 50:50 to 97:3,
d.r. = 1.5:1 to 16:1), depending on the ring size as well as the
a-EWG of the nucleophile in a subtle way. The d.r. values of
3aa–ac (16:1 to 4:1) declined gradually with an increase in the
ring size of the cyclic ketone moiety on the corresponding b-
ketoesters 2a–c. The reactions of cyclopentanone-based b-
ketoesters (2a and 2d–f) afforded the corresponding products
(3aa, 3ad, 3ae and 3af) with b/l ratios ranging from 88:12 to
95:5, apparently affected by their distinct ester moieties. The
genation of 3aa gave 5, bearing three contiguous stereocen-
ters, in good yield with greater than 99% ee for the major
diastereomer. Treatment of 3aa with phenylhydrazine under
acidic conditions provided rapid access to the tricyclic indole
derivative 6 in 52% yield without loss of enantioselectivity.
Borohydride reduction of 3aa furnished the bicyclic lactone 7,
bearing an exo-methylene moiety, in 93% yield with greater
than 20:1 d.r. and greater than 99% ee. Finally, dihydrox-
ylation of 3aa followed by acidic workup provided the
hemiketal 8 with greater than 20:1 d.r. and greater than 99%
ee.
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Considering the bifunctional role of SKPs in the allylic
substitution of MBH acetates,[11] as well as the sense of
asymmetric induction in the titled reaction, a schematic
representation of the stereocontrol model is proposed in
Figure 1. In the key intermediate,[11b] one of the phenyl rings
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Figure 1. Stereoselectivity control model and X-ray structure for (R,R)-
3ja. Thermal ellipsoids shown at 30% probability.
on the phosphonium moiety effectively blocks the backside of
the h2-Pd-allyl moiety, thus suggesting that the outer-sphere
mechanism is unlikely to be feasible. The stereochemical
outcome can be explained by a s-p-s isomerization of the
complex, followed by an inner-sphere 3,3’-reductive elimina-
tion[14] of the resulting h1-allyl-h1-enolatopalladium, thus
yielding (R,R)-3aa as the major isomer.[15]
In summary, we have developed the first palladium-
catalyzed asymmetric construction of the vicinal tertiary and
all-carbon quaternary stereocenters by allylic alkylation of b-
dicarbonyl compounds with MBH adducts. The SKP ligand
turns out to be critically important in the catalysis, thus
affording a wide variety of densely functionalized products in
high yields with excellent enantioselectivities, and good to
high regio- and diastereoselectivities. The synthetic utility of
the protocol was exemplified in a number of transformations
which allow rapid access to a variety of polyfunctionalized
structures with rich stereocenters.
[5] B. M. Trost, J. R. Miller, C. M. Hoffman, Jr., J. Am. Chem. Soc.
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Acknowledgments
We are grateful for financial support from MOST
(2016YFA0202900), NSFC (21232009, 20421091), and CAS
(QYZDY-SSW-SLH012, XDB20000000).
[10] a) X. Wang, Z. Han, Z. Wang, K. Ding, Angew. Chem. Int. Ed.
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Conflict of interest
The authors declare no conflict of interest.
Keywords: allylic compounds · asymmetric catalysis ·
palladium · P ligands · spiro compounds
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Wang, K. Ding, J. Am. Chem. Soc. 2014, 136, 405; c) J. Liu, Z.
Brozek, J. P. Morken, J. Am. Chem. Soc. 2010, 132, 10686;
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11806, and references therein. See also ref. [11d].
[15] CCDC 1518689 and 1527618 (R,R)-3ja and (R,R,S)-7, contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
[12] H. Mayr, Tetrahedron 2015, 71, 5095.
[13] Privileged Chiral Ligands and Catalysts (Ed.: Q.-L. Zhou),
Wiley-VCH, Weinheim, 2011.
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mechanism. See: a) H. Nakamura, K. Aoyagi, J.-G. Shim, Y.
Yamamoto, J. Am. Chem. Soc. 2001, 123, 372; b) N. H. Sherden,
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Manuscript received: February 9, 2017
Final Article published: && &&, &&&&
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Communications
Allylic Compounds
J. Liu, Z. Han, X. Wang, F. Meng,
Z. Wang,* K. Ding*
&&&& — &&&&
Palladium-Catalyzed Asymmetric
Construction of Vicinal Tertiary and All-
Carbon Quaternary Stereocenters by
Allylation of b-Ketocarbonyls with
Morita–Baylis–Hillman Adducts
SKP/Pd systems go: An SKP/Pd system
demonstrates unique catalytic perfor-
mance in construction of vicinal tertiary
and all-carbon quaternary stereodyads by
allylic alkylation of b-ketocarbonyls with
Morita–Baylis–Hillman adducts. Thus
a wide range of densely functionalized
products are delivered with high regio-,
diastereo-, and enantioselectivities.
6
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