Palladium(0)-Lithium Iodide Cocatalyzed Asymmetric Hydroalkylation of Conjugated Enynes with Pronucleophiles Leading to 1,3-Disubstituted Allenes

Article abstract of DOI:10.1021/acs.orglett.9b02439

Axially chiral 1,3-disubstituted allenes were synthesized via hydroalkylation of alkyl- or aryl-substituted conjugated enynes (readily prepared via a Sonogashira reaction) with pronucleophiles such as dimethyl malonate under the cocatalysis of DTBM-SEGPHOS-ligated palladium and lithium iodide. Although the palladium catalyst ligated with (S)-DTBM-SEGPHOS prefers the formation of (R)-1,3-disubstituted allenes, lithium iodide recovers and increases the intrinsic selectivity producing (S)-allenes by promoting the isomerization of the exo-alkylidene-π-allylpalladium intermediate prior to the nucleophilic substitution step.

Full text of DOI:10.1021/acs.orglett.9b02439

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Palladium(0)−Lithium Iodide Cocatalyzed Asymmetric
Hydroalkylation of Conjugated Enynes with Pronucleophiles
Leading to 1,3-Disubstituted Allenes
,
†,‡
†
†
†
Hirokazu Tsukamoto,*
Tatsuya Konno, Kazuya Ito, and Takayuki Doi
†
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Department of Pharmaceutical Sciences, Yokohama University of Pharmacy, 601 Matano-cho, Totsuka-ku, Yokohama 245-0066,
‡
Japan
*
S Supporting Information
ABSTRACT: Axially chiral 1,3-disubstituted allenes were synthesized via hydroalkylation of alkyl- or aryl-substituted
conjugated enynes (readily prepared via a Sonogashira reaction) with pronucleophiles such as dimethyl malonate under the
cocatalysis of DTBM-SEGPHOS-ligated palladium and lithium iodide. Although the palladium catalyst ligated with (S)-DTBM-
SEGPHOS prefers the formation of (R)-1,3-disubstituted allenes, lithium iodide recovers and increases the intrinsic selectivity
producing (S)-allenes by promoting the isomerization of the exo-alkylidene-π-allylpalladium intermediate prior to the
nucleophilic substitution step.
1
,3-Disubstituted allenes with axial chirality are found in
Scheme 1. Transformation of exo-Alkylidene-π-
allylpalladium 3 Generated from 3-Bromo-1,3-alkadiene 1,
2,3-Alkadienyl Acetate or Phosphate 2, and Conjugated
Enyne 3 into Chiral 1,3-Disubstituted Allene 6
1
biologically active natural products and pharmaceuticals. Chiral
allenes are also useful synthetic intermediates because a wide
variety of reactions can be used to transfer the axial chirality to
2
point chirality in the product. Optically active allenes can be
conventionally synthesized using an S 2′ reaction of chiral
N
propargyl alcohol derivatives, which are typically prepared via
optical resolution of their acetate derivatives or the asymmetric
3
reduction of their corresponding ketones. On the other hand,
chiral allene 6 can be obtained from achiral or racemic substrates
(
1 and 2) bearing a leaving group through exo-alkylidene-π-
allylpalladium intermediate 3 ligated with a chiral phosphine
ligand (Scheme 1).
4
−6
However, the preparation of 1 and 2
requires multiple steps from commercially available materials
and their transformation into allene 6 requires a stoichiometric
amount of base, leading to the formation of salts as byproducts.
To solve these problems, we planned to generate intermediate 3
7
palladation) of the alkyne, and (3) reductive coupling, although
any proof such as stereochemical information to support this
mechanism was not given. Herein, we report effective reaction
conditions for the palladium(0)-catalyzed asymmetric hydro-
alkylation of internal conjugated enynes 7 with pronucleophiles,
from conjugated enyne 7 via hydropalladation, i.e., the
concomitant protonation and oxidative addition to palladi-
um(0) (vide infra). Enyne 7 can be readily prepared using a
Sonogashira reaction between a terminal alkyne and vinyl
bromide, and undergo the addition of pronucleophiles 5 under
neutral conditions. Yamamoto’s group reported the synthesis of
achiral 1-substituted or 1,1-disubstituted allenes via a related
coupling reaction between 1-alkenyl-substituted terminal
alkynes and cyano-containing pronucleophiles in the presence
of Pd dba ·CHCl and 1,1′-bis(diphenylphosphino)ferrocene
9
−11
such as substituted and unsubstituted malonates.
We also
prove that the 1,4-addition of a proton and the carbonucleophile
occurs with syn-selectivity via a predominant anti-hydro-
palladation step and subsequent nucleophilic substitution with
inversion of stereochemistry.
2
3
3
8
(
dppf) in THF. They also proposed a reaction mechanism
consisting of (1) oxidative addition of the pronucleophile to
palladium(0), (2) regioselective hydropalladation (or carbo-
Received: July 14, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b02439
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Initially, the reaction conditions for the hydroalkylation of
internal alkyne 7a with dimethyl malonate (5A) were screened
Table 1). The reactions were performed using 5A (3.0
contrast to Ogasawara and Hayashi’s work, the use of
dibenzylideneacetone-ligated palladium complexes did not
increase the enantioselectivity (entries 2 and 3). The addition
of a catalytic amount of salt was examined because the low and
opposite enantioselectivity observed in our reaction may be
derived from its salt-free conditions. Neither lithium acetate,
which was employed by Nemoto and Hamada for the
asymmetric substitution reaction of 2,3-alkadienyl phosphate,
nor its potassium salt improved the enantioselectivity (entries 4
and 5). However, the addition of lithium halides reversed the
enantioselectivity to give product 6aA with the (S)-enantiomer
obtained as the major component (entry 1 vs entries 6−8). At
this point, the enantioselectivity of the hydroalkylation of 7a
with 5A was identical to that of the palladium-catalyzed
(
Table 1. Optimization of the Asymmetric Hydroalkylation of
a with 5A
7
5
,6
substitution reaction using 1a and 2a. The enantioselectivity
of the reaction with lithium iodide was further improved by
decreasing the reaction temperature to 50 °C (entry 8 vs 9). The
catalyst loading can be decreased to 5 mol % without any
significant reduction in the yield and enantioselectivity (entry
Temp
Yield
a
Er (S/R)
b
Entry
1
Pd catalyst
(allyl)CpPd
Additive
none
(°C)
(%)
(%)
65
65
65
65
65
65
65
65
50
50
50
rt
nd (81)
29:71
33:67
28:72
28:72
25:75
68:32
76:24
78:22
83:17
86:14
84:16
86:14
85:15
(
10 mol %)
Pd dba ·CHCl
3
2
3
4
5
6
7
8
9
none
nd (83)
2
3
1
0). The additive can also be reduced to the same amount as the
(
5 mol %)
palladium catalyst with little effect on the enantioselectivity
(entries 10−13). The reaction proceeded even at room
temperature (entry 12).
Pd(dba)2
none
nd
(quant)
(
10 mol %)
(allyl)CpPd
LiOAc
(30 mol %)
KOAc
(30 mol %)
LiCl
(30 mol %)
LiBr
(30 mol %)
LiI
(30 mol %)
LiI
(30 mol %)
LiI
(30 mol %)
94 (78)
100 (78)
95 (77)
93 (81)
nd (90)
95
(
10 mol %)
Using the optimized conditions shown in Table 1, entry 13,
the scope of the conjugated enyne substrate and pronucleophile
(allyl)CpPd
10 mol %)
(
t
was explored (Figure 1). Enynes 7b−d (R = Cy, Ph, and Bu)
(allyl)CpPd
10 mol %)
(
(allyl)CpPd
10 mol %)
(
(allyl)CpPd
10 mol %)
(
(allyl)CpPd (10
mol %)
10
11
12
13
(allyl)CpPd
99
(
5 mol %)
(allyl)CpPd
5 mol %)
LiI
(15 mol %)
LiI
(15 mol %)
quant
(
(allyl)CpPd
5 mol %)
quant
(
(allyl)CpPd
5 mol %)
LiI (5 mol %)
50
98 (84)
(
a
1
The yield was determined using H NMR spectroscopy with 1,1,2,2-
Figure 1. Scope of conjugated enynes 7b−d and pronucleophiles 5A−
G investigated in the hydroalkylation reaction.
tetrachloroethane as an internal standard. The isolated yields are
shown in the parentheses. The enantiomeric ratio was determined
b
using chiral HPLC.
substituted with secondary and tertiary alkyl, and aryl groups at
the alkyne terminus, also underwent the asymmetric hydro-
alkylation with 5A to afford allenes 6(b−d)A in excellent yield.
The enantioselectivities of the products were much higher than
those observed for octyl-substituted enyne 7a. A substituent at
C-2 in dimethyl malonate was tolerated to give corresponding
allenes 6d(B−D) in moderate to good yield with high
enantioselectivity. Bis(phenylsulfonyl)methane (5E) also par-
ticipated in the enantioselective conversion of 7b and 7d into
1,3-disubstituted allenes 6bE and 6dE, respectively. Both the
reaction yield and optical purity of allenes 6bF and 6bG
prepared via the hydroalkylation of 7b with acetylacetone (5F)
and malononitrile (5G) were lower than those observed for 6bA
and 6bE.
To obtain insight into the stereochemistry of the hydro-
alkylation reaction of enyne 7 with pronucleophile 5A,
deuterium-labeled enyne 7b-d with an E-configuration was
prepared and subjected to the reaction using achiral diphosphine
ligand 8 in the absence of lithium iodide (Scheme 2). The
resulting product 6bA-d was obtained as a 3:1 diastereomeric
1
2
equiv), allyl(cyclopentadienyl)palladium(II) (10 mol %),
and a variety of diphosphine ligands (15 mol %) at 65 °C in
methanol, which we expected to function as a proton source.
Among achiral and chiral bis(diarylphosphine) ligands we tested
(
see Supporting Information), axially chiral SEGPHOS bearing
electron-rich bis(3,5-di-tert-butyl-4-methoxyphenyl, DTBM)
groups on the phosphorus atoms gave 6aA in good yield
entry 1). Interestingly, the major enantiomer of product 6aA
obtained using the (S)-DTBM-SEGPHOS did not match that
prepared via the substitution reaction of 3-bromo-1,3-dienes 1a
R = octyl) and 2,3-alkadienyl phosphate 2a (R = octyl, X =
OPO(OEt) ) with 5A using the (S)-biaryl-based ligand in the
presence of Pd dba .
enantioselectivity using the DTBM-SEGPHOS ligand, the
reaction conditions were further optimized by testing different
palladium sources and additives that can promote the isomer-
ization between the two exo-alkylidene-π-allylpalladium species
(
(
2
5
,6
To improve (or reverse) the
2
3
(
3 and 3′) via coordination and stabilization of alkenyl
13
intermediate 4 (Scheme 1) (Table 1, entries 2−13). In
B
DOI: 10.1021/acs.orglett.9b02439
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 2. syn-Selective Hydroalkylation of 7b-d with 5A
hydroalkylation of enyne 7a in the absence of lithium iodide
shows that, in the initial hydropalladation step, the chiral
diphosphine ligand prefers the formation of the opposite exo-
alkylidene-π-allylpalladium species, which leads to the minor
enantiomer and that the nucleophilic substitution step precedes
the isomerization process.
Scheme 3. Overall Retention of Stereochemistry Observed in
the Substitution Reaction of 2b-d with 5A and the Effect of
Lithium Iodide on the Chirality Transfer Pathway
1
mixture, which was determined using H NMR analysis of γ-
lactones 10-d and 11-d prepared from 6bA-d via saponification
of the methyl ester groups, decarboxylation, and stereoselective
14
iodolactonization using the procedure of Ma. The stereo-
chemistries of 10-d and 11-d were established by their NOESY
spectra. While the methine proton at γ-position in 10-d had
NOE with the vinyl proton and no NOE with the major residual
proton as X at the β-position, the γ-proton in 11-d had NOE
with the major residual proton as X and no NOE with the vinyl
proton. The chemical shifts of geminal protons at β-positions in
1
0-d and 11-d also agreed with those reported for γ-vinyl-γ-
butyrolactone, where the vinyl group shielded and deshielded
15
the cis- and trans-protons, respectively. These assignments
established the stereochemistry of 6bA-d, as shown in Scheme 2.
The diastereoselectivity observed in the hydroalkylation
reaction indicates that the 1,4-addition of the proton and
nucleophile (deprotonated 5A) to 7b-d occurred with syn-
selectivity.
The exo-alkylidene-π-allylpalladium intermediate generated
via hydropalladation of conjugated enyne 7b-d in the presence of
pronucleophile 5A can also be formed in the substitution
reaction of 2,3-alkadienyl carbonate 2b-d with 5A via oxidative
addition of 2b-d to the palladium(0) complex, decarboxylation,
and deprotonation of pronucleophile 5A. An overall retention of
the configuration was observed in the substitution reaction of
In summary, we have developed a palladium(0)−lithium
iodide cocatalyzed hydroalkylation reaction to synthesize axially
chiral 1,3-disubstituted allenes from conjugated enynes, which
are readily prepared via a Sonogashira reaction between a
terminal alkyne and vinyl bromide. The reaction does not need
the addition of a stoichiometric amount of additive or produce
any byproducts. The reaction proceeds via a syn-selective 1,4-
addition of a proton and nucleophile to the conjugated enyne,
which is derived from an anti-hydropalladation step followed by
nucleophilic substitution with inversion of stereochemistry. A
mechanistic study on the anti-selective hydropalladation step is
currently underway in our laboratory.
2
b-d with 5A with achiral ligand 8 in the absence of lithium
iodide (Scheme 3), which indicated that the oxidative addition
and nucleophilic substitution steps should occur via a double
inversion of stereochemistry, as observed in the Tsuji−Trost
reaction. This result strongly supports that the syn-selective
hydroalkylation was initiated by a preferential anti-hydro-
palladation step, i.e., anti-protonation of the conjugated enyne
ASSOCIATED CONTENT
Supporting Information
■
1
6
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.orglett.9b02439.
17
coordinated by electron-rich palladium(0). The syn-selectivity
Detailed experimental procedures, spectroscopic data,
and copies of NMR spectra (PDF)
observed in the hydroalkylation reaction of conjugated enyne
7b-d is also potentially consistent with the reaction mechanism
proposed by Yamamoto, i.e., the oxidative addition of the
pronucleophile to palladium(0) followed by syn-hydropallada-
tion and reductive elimination. However, soft carbonucleophiles
rarely undergo reductive elimination with retention of stereo-
AUTHOR INFORMATION
Corresponding Author
■
*
E-mail: hirokazu.tsukamoto@hamayaku.ac.jp.
ORCID
1
6
chemistry.
In addition, chirality transfer of (S ,R)-2b-d into 6bA-d was
a
Hirokazu Tsukamoto: 0000-0002-7849-6427
Takayuki Doi: 0000-0002-8306-6819
Notes
insufficient and was completely lost upon the addition of lithium
iodide (Scheme 3). A lack of chirality transfer is required for the
dynamic kinetic asymmetric substitution reaction of 2,3-
alkadienyl phosphate 2 and the asymmetric hydroalkylation of
The authors declare no competing financial interest.
7
. This result was consistent with the hypothesis that the
ACKNOWLEDGMENTS
additive can improve the enantioselectivity of the reaction by
promoting the isomerization between exo-alkylidene-π-allylpal-
ladium species 3 and 3′ via stabilization of alkenyl intermediate 4
■
This work was partly supported by The Research Foundation for
Pharmaceutical Sciences, SUNTRY FOUNDATION for LIFE
SCIENCES, Platform Project for Supporting Drug Discovery
(Scheme 1). The reverse enantioselectivity observed in the
C
DOI: 10.1021/acs.orglett.9b02439
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
and Life Science Research (Basis for Supporting Innovative
Drug Discovery and Life Science Research (BINDS)) from
AMED under Grant Number JP18am0101095 and
JP18am0101100, and JSPS KAKENHI Grant Numbers
JP19K06966 and JP15H05837 in Middle Molecular Strategy.
M.; Kadota, I.; Saito, S.; Yamamoto, Y. Tetrahedron 1997, 53, 9097−
9106.
(9) A related series of asymmetric hydrometalation of conjugated
enynes have been reported. Hydroboration: (a) Matsumoto, Y.; Naito,
M.; Uozumi, Y.; Hayashi, T. J. Chem. Soc., Chem. Commun. 1993, 1468−
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L.; Yu, S.; Ge, S. Org. Chem. Front. 2018, 5, 1284−1287. (d) Huang, Y.;
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DOI: 10.1021/acs.orglett.9b02439
Org. Lett. XXXX, XXX, XXX−XXX