An Enantioselective Multicomponent Carbonyl Allylation of Aldehydes with Dienes and Alkynyl Bromides Enabled by Chiral Palladium Phosphate

Article abstract of DOI:10.1002/adsc.201700621

An enantioselective multicomponent carbonyl allylation reaction of 1,3-butadienes, alkynyl bromides and aldehydes has been established, leading to the generation of densely functionalized homoallylic alcohols in high levels of structural diversity and stereoselectivity. The multicomponent process sequentially comprises the oxidative addition, salt metathesis, insertion/π-allyl-Pd formation, asymmetric allylic borylation, and enantioslecitve carbonyl allylborylation, wherein the alkynyl palladium phosphate in situ generated from the chiral silver phosphate and the alkynyl palladium bromide turns out to be a key intermediate that allows the efficient stereochemical control. (Figure presented.).

Full text of DOI:10.1002/adsc.201700621

Title: An Enantioselective Multicomponent Carbonyl Allylation of
Aldehydes with Dienes and Alkynyl Bromides Enabled by Chiral
Palladium Phosphate
Authors: Liu-zhu Gong, Hong-Cheng Shen, Pu-Sheng Wang, Zhong-
Lin Tao, and Zhi-Yong Han
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700621
Link to VoR: http://dx.doi.org/10.1002/adsc.201700621

10.1002/adsc.201700621
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
An Enantioselective Multicomponent Carbonyl Allylation of Aldehydes
with Dienes and Alkynyl Bromides Enabled by Chiral Palladium
Phosphate
Hong-Cheng Shena, Pu-Sheng Wanga, Zhong-Lin Taoa, Zhi-Yong Hana, Liu-Zhu
Gonga*
a
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science
and Technology of China, Hefei 230026, PR China
Fax: (+86)-551-360-6266; e-mail: gonglz@ustc.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Scheme 1. General strategies for asymmetric carbonyl
allylation with 1,3-dienes.
Abstract: An enantioselective multicomponent carbonyl
allylation reaction of 1,3-butadienes, alkynyl bromides and
aldehydes has been established, leading to the generation of
densely functionalized homoallylic alcohols in high levels
of structural diversity and stereoselectivity. The
multicomponent process sequentially undergoes the
oxidative addition, salt metathesis, insertion/-allyl-Pd
formation,
asymmetric
allylic
borylation,
and
enantioslecitve carbonyl allylborylation, wherein the
alkynyl palladium phosphate in situ generated from the
chiral silver phosphate and the alkynyl palladium bromide
turns out to be a key intermediate that allows the efficient
stereochemical control.
Keywords: Asymmetric catalysis, Carbonyl allylation,
Chiral palladium phosphate, Homoallylic acohols, 1,3-
Butadiene
One desirable scenario would involve the use of
easily accessible 1,3-dienes as allylating reagent
precursor to access a diverse range of either carbon–
carbon or carbon–heteroatom bonds.[4] By exploiting
a ruthenium catalyst modified by a chiral phosphate
counterion, Krische and co-workers established a
highly atom-economic direct redox-triggered carbon-
carbon coupling of alcohols and 1,3-butadienes
(Scheme 1a).[5] Most recently, our group
accomplished a highly selective multicomponent
Stereoselective allylation of carbonyl compounds
has been accepted one of the most important but
challenging transformations in organic synthesis.[1]
The resulting chiral homoallylic alcohols have been
shown to be among the most valuable building blocks
allowing for the synthesis of a wide scope of
biologically
active
natural
products
and
pharmaceuticals.[2] For decades, numerous strategies
have been developed for the stereoselective allylation
of carbonyl compounds. Among them, the domino
multicomponent allylation reaction (MCAR) of
carbonyl compounds with allylic reagent precursors
is one of the most versatile strategy to increase the
structural complexity[2b] and more importantly, has
typical features of ideal synthesis.[3] However,
multiple bond breaking and forming events,
simultaneously or sequentially occurring in the
MCAR to assemble structurally complex and densely
functionalized homoallylic alcohols from readily
available starting materials in a single operation and
stereochemical control manner, turn out to be greatly
more challenging than single step reactions.
carbonyl allylation reaction of
1,3-dienes,
aryldiazonium tetrafluoroborates, and aldehydes
under the combined catalysis of a palladium complex
and chiral anion phase transfer,[6] producing Z-
configured chiral homoallylic alcohols in high yields
and enantioselectivity (Scheme 1b).[7] However,
suffering from stability and availability of
organodiazonium tetrafluoroborates other than
aryldiazonium, the protocol is only able to introduce
an aryl group to final products. Thus, efficient
tranformations capable of replacing aryldiazonium
with other substrates are highly desired.
1
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10.1002/adsc.201700621
Advanced Synthesis & Catalysis
Alkynes are synthetic moieties showing
phosphoric acid 9c appeared to be promising additive
in terms of stereoselectivity (entries 6-8).
Interestingly, chiral silver phosphate 9d delivered a
higher enantiomeric excess (entry 9). Especially, a
slightly enhanced enantioselectivity was obtained
when the aldehyde 3a was added after the borylation
reaction was complete (entry 10). Notably, the
catalyst loading could be reduced in a small amount
without sacrificing the outcomes (entry 11).
considerable influence in materials, biological, and
medicinal science as they can be utilized as pivotal
handles for further transformations.[8] An alkynyl
bromide is able to undergo oxidative addition with a
palladium(0) complex under mild conditions to
generate an alkynyl palladium bromide I (Scheme
2).[9] We envisaged that the alkynyl palladium
bromide I would be able to undergo a salt metathesis
reaction with a chiral silver phosphate to afford chiral
palladium(II) phosphate II,[10] which then undergoes a
Heck insertion reaction with a 1,3-butadiene to form
a chiral allylic palladium intermediate III that is
subsequently transformed into π-allyl palladium
phosphate IV.[3a,6,11] The π-allyl palladium phosphate
IV will undergo an asymmetric counteranion directed
catalytic[12] borylation to generate a chiral allyl borate
Table 1. Optimization of Reaction Conditions[a]
V
or V’, which undergoes the asymmetric
allylborylation of aldehydes to homoallylic
alcohols,[7] and to release boron phosphate VI, which
is able to react with silver salt base to regenerate
silver phosphate (AgX*) for the next catalytic cycle.
Herein, we will describe the use of such a concept to
create a highly selective multicomponent carbonyl
allylation reaction of 1,3-butadienes, alkynyl
bromides and aldehydes for the synthesis of densely
functionalized chiral Z-configured homoallylic
alcohols.
yield
(%)[b]
5aaa
/6aaa[c]
ee
(%)[e]
entry
1a/2a/3a/4a
9
Z/E[d]
9a
9a
9a
9a
9a
9a
9b
9c
9d
9d
9d
1f
1/1/1/1
1/1/1/1
1/1/1/1
1/1/1/1
2/2/1/2
4/2/1/2
4/2/1/2
4/2/1/2
4/2/1/2
4/2/1/2
4/2/1/2
-
-
-
-
2g
25
46
42
87
99
92
99
95
99
99
2.5/1
5/1
6/1
5/1
6/1
5/1
6/1
6/1
6/1
6/1
9/1
36
88
87
86
87
75
88
90
91
91
Scheme 2. Mechanistic hypothesis to account for the
possibility of asymmetric multicomponent carbonyl
allylation reaction.
3h
>20/1
>20/1
18/1
>20/1
19/1
>20/1
>20/1
>20/1
>20/1
4h,i
5h,i
6h,i
7h,i
8h,i
9h,i
10h-j
11h-k
[a] Unless noted otherwise, the reaction of 1a (0.1 mmol), 2a (0.1
mmol), 3a (0.1 mmol), and 4a (0.1mmol) were carried out with
Pd(OAc)2 (0.01 mmol), 9 (0.02 mmol) and Inorganic base (0.1 mmol) in
In the presence of catalytic amounts of Pd(OAc)2
and chiral phosphoric acid 9a,[13]
the
o
toluene (2.0 mL) at 25 C for 48 h. [b] Isolated yield. [c] The ratio of
multicomponent reaction of (E)-1-phenylbutadiene
(1a), (bromoethynyl)benzene (2a), 4-nitrobenz-
aldehyde (3a) and a diborate 4a was initially carried
out in toluene with AgOAc as base (Table 1, entry 1).
Unfortunately, the proposed reaction failed to give
the desired homoallylic alcohol product. Then, other
silver salt bases were tested and found that both silver
fluoride and silver carbonate rendered the desired
reaction to proceed while silver carbonate allowed a
higher stereoselectivity (entries 2 and 3). Lowering
the concentration and increasing the amounts of 1a,
2a and 4a (entries 4-6) enabled the reaction to give
99% yield, 6:1 regiomeric ratio (5aaa/6aaa), Z/E >
20:1 and 87% ee. The evaluation of chiral Brønsted
acids revealed that the sterically congested
5aaa/6aaa was determined by 1H-NMR analysis of the crude
products.[d] The ratio of (Z)-5a/(E)-5a was determined by 1H-NMR
analysis of the crude products. [e] The ee value of (Z)-5a was determined
by HPLC analysis. [f] Inorganic base: AgOAc; [g] Inorganic base: AgF;
[h] Inorganic base: Ag2CO3; [i] 4.0 mL toluene was used in total. [j] 3a
was added after the mixture was stirred for 24 h, and then stirred for
another 24 h. [k] 7.5 mol% of Pd(OAc)2 and 15 mol% of 9d were used.
Under the optimal reaction conditions, the
generality for 1,3-butadiene component was first
examined by the reaction with 2a and 3a (Table 2).
The diene substrates bearing an ortho-substituted
phenyl group provided the desired products in high
yields with excellent regio- and Z/E-selectivitives,
2
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10.1002/adsc.201700621
Advanced Synthesis & Catalysis
and good enantioselectivities (entries 1-3). Other
dienes with either meta- or para-substituted aryl
group also resulted in good yields, Z/E- and
enantioselectivities, albeit with a relatively lower
regioselectivity (entries 4-8). Notably, the installation
of substituent at C3 of diene was allowed and gave a
homoallylic alcohol in high yield and with good
regio-, Z/E-, and enantioselectivities (entry 9), while
the extension of the optimal reaction conditions to an
alkyl diene could only afford the desired product in
moderate results (entry 10). The configuration of
5daa was assigned to be (1R, 2S) by comparing
HPLC retention time with a known compound after
derivation.[14]
Table 3. Scope with respect to 1-bromo alkynes[a]
yield
(%)[b]
ee
(%)[e]
entry
R
5/6[c]
Z/E[d]
2
5
1
2-MeC6H4
3-MeC6H4
3-FC6H4
91
98
99
99
99
86
99
85
85
66
>20:1 >20:1 89
>20:1 >20:1 92
>20:1 >20:1 93
>20:1 >20:1 91
>20:1 >20:1 91
>20:1 >20:1 92
>20:1 >20:1 89
>20:1 >20:1 91
>20:1 >20:1 76
>20:1 >20:1 84
2b 5bba
2c 5bca
2d 5bda
2
3
4
3-ClC6H4
4-MeC6H4
4-iPrC6H4
4-BrC6H4
4-MeO2CC6H4
2-thienyl
2e
2f
5bea
5bfa
Table 2. Scope of 1,3-Butadienes[a]
5
6
2g 5bga
2h 5bha
7
8
2i
2j
5bia
5bja
9
10
cyclohexyl
2k 5bka
ee
(%)[e]
yield
entry
R
1
5
5/6[c]
Z/E[d]
(%)[b]
[a] Reactions of 1 (0.40 mmol), 2a (0.20 mmol), 3a (0.10 mmol), and 4a
(0.20mmol) were carried out with Pd(OAc)2 (0.0075 mmol), 9d (0.015
mmol), and Ag2CO3 (0.1 mmol) in toluene (4.0 mL) at 25 oC. 3a in
toluene (2.0 mL) was added after the mixture was stirred for 24 h, then
stirred for another 24h. [b] Isolated yield. [c] The ratio of 5/6 was
>20:
>20:
1
2-MeC6H4
2-MeOC6H4
2-BrC6H4
3-MeC6H4
3-ClC6H4
99
99
93
99
86
99
99
95
99
70
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
18:1
93
84
84
90
90
91
92
92
84
79
1b
1c
1d
1e
1f
5baa
5caa
5daa
5eaa
5faa
5gaa
5haa
5iaa
2
1
>20:
3
1
1
8:1
determined by H-NMR analysis of the crude products. [d] The ratio of
4
1
(Z)-5/ (E)-5 was determined by H-NMR analysis of the crude products.
[e] The ee value of (Z)-5 was determined by HPLC analysis.
5
4:1
7:1
6:1
4:1
16:1
1:1
6
4-MeC6H4
4-MeOC6H4
4-FC6H4
1g
1h
1i
Finally, the substrate scope of the multicomponent
allylation reaction with respect to aldehydes was explored
(Table 4). A wide spectrum of aromatic aldehydes were
accommodated to give homoallylic alcohols in very high
yields and with excellent levels of regio-, enantio-, and
Z/E-selectivities. The multicomponent reaction of
unsaturated aldehydes also proceeded with excellent
results (entry 7). An aliphatic aldehyde was nicely
tolerated to furnish a chiral homoallylic alcohol with
almost perfect yields, as well as regio- and Z/E-selectivities
(entry 8). In addition, formaldehyde underwent the
multicomponent allylation reaction to give a chiral
homoallylic alcohol with excellent selectivities (entry 9).
7
8
9
1j
5jaa
5kaa
10
cyclohexyl
>20:1
1k
[a] Reactions of 1 (0.40 mmol), 2a (0.20 mmol), 3a (0.10 mmol), and 4a
(0.20mmol) were carried out with Pd(OAc)2 (0.0075 mmol), 9d (0.015
mmol), and Ag2CO3 (0.1 mmol) in toluene (2.0 mL) at 25 oC. 3a in
toluene (2.0 mL) was added after the mixture was stirred for 24 h, then
stirred for another 24h. [b] Isolated yield. [c] The ratio of 5/6 was
1
determined by H-NMR analysis of the crude products. [d] The ratio of
1
(Z)-5/ (E)-5 was determined by H-NMR analysis of the crude products.
[e] The ee value of (Z)-5 was determined by HPLC analysis.
The generality for alkynyl bromides was then
investigated (Table 3). A broad scope of aryl alkynyl
bromides were nicely tolerated to give the desired
products in high yields and with excellent levels of
regio- and setereoselectivities (entries 1-8). A
heteroaryl alkynyl bromide smoothly underwent the
reaction to offer a high yield, but a modest
enantioselectivity (entry 9). An aliphatic alkynyl
bromide also participated in the reaction and
furnished a chiral homoallylic alcohol with excellent
selectivities (entry 10).
To demonstrate the practical use of this asymmetric
multicomponent allylation reaction, a scale-up reaction of
1b, 2h and 3a was conducted with diborate 4a and with
Ag2CO3 as base in the presence of Pd(OAc)2 and 9d,
delivering the chiral homoallylic alcohol 5bha in 87%
yield, >20:1 Z/E and 85% ee (eq. 1).
3
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10.1002/adsc.201700621
Advanced Synthesis & Catalysis
Table 4. Scope with respect to aldehydes[a]
process proceeds via sequential reactions including
oxidative addition, salt metathesis, insertion/-allyl-Pd
formation, asymmetric allylic borylation, and asymmetric
carbonyl allylborylation, wherein the alkynyl palladium
phosphate in situ generated from the metathesis reaction of
the chiral silver phosphate and the alkynyl palladium
bromide turns out to be a key intermediate that allows the
efficient stereochemical control. The process shows
excellent generality for the reaction components and is
able to deliver densely functionalized homoallylic alcohols
in high levels of structural diversity and stereoselectivity.
yield
(%)[b]
ee
(%)e
entry
R
5/6c
Z/Ed
3
5
1
2
3
4
5
6
7
C6H5
99
94
97
99
81
83
99
>20:1 >20:1 90
>20:1 >20:1 94
>20:1 >20:1 91
>20:1 >20:1 91
>20:1 >20:1 91
>20:1 >20:1 88
>20:1 >20:1 90
3b 5bab
3c 5bac
3d 5bad
4-MeC6H4
4-MeOC6H4
2-naphthyl
2-furanyl
2-thienyl
Experimental Section
3e
3f
5bae
5baf
General procedure for the asymmetric
multicomponent carbonyl allylation reaction
3g 5bag
3h 5bah
To a flame-dried and Ar-purged Schlenk tube (25 mL)
were added Pd(OAc)2 (0.0075 mmol, 1.7 mg), 9d (0.015
mmol, 16.7 mg), diborate 4a (0.2 mmol, 150.2 mg), silver
carbonate (0.1 mmol, 27.6 mg) and a stir bar. The
Schlenktube was then evacuated and filled with argon.
This cycle was repeated three times and followed by
(E)-
PhCH=CH
PhCH2CH2
8
9
93
45
>20:1 >20:1 92
>20:1 >20:1 92
3i
5bai
H
3k 5baj
addition
of
1,3-diene
1
(0.4
mmol)
and
[a] Reactions of 1 (0.40 mmol), 2a (0.20 mmol), 3a (0.10 mmol), and 4a
(0.20mmol) were carried out with Pd(OAc)2 (0.0075 mmol), 9d (0.015
mmol), and Ag2CO3 (0.1 mmol) in toluene (4.0 mL) at 25 oC. 3a in
toluene (2.0 mL) was added after the mixture was stirred for 24 h, then
stirred for another 24h. [b] Isolated yield. [c] The ratio of 5/6 was
(bromoethynyl)benzene 2 (0.2 mmol) in toluene (2.0 mL)
via syringe. The mixture was stirred at 25℃ for 24h and
then aldehyde 3 (0.1 mmol) in toluene (2.0 mL) was add
by syringe. The mixture was stirred at 25℃ for 24h again.
After that, the reaction was quenched by the addition of
2M NaOH (1 mL) and the aqueous layer was extracted
with EtOAc (3 x 10 mL). The combined organic layers
were dried over anhydrous Na2SO4 and then concentrated
under vacuum. The residue was purified by flash column
chromatography (petroleum ether / DCM = 1:3) on silica
1
determined by H-NMR analysis of the crude products. [d] The ratio of
1
(Z)-5/ (E)-5 was determined by H-NMR analysis of the crude products.
[e] The ee value of (Z)-5 was determined by HPLC analysis.
To explain the observed stereochemistry of the
asymmetric allylation reaction, plausible transition states
were proposed. The chiral allylic borate generated from the
palladium-catalyzed propargyl borylation of diene was
identified to have a (R)-configured stereogenic center.[15] It
reacts with aldehyde basically via chair-like transition
states. Although TS-I features an unfavorable allylic
interactions due to the pseudo-axial position of the
propargylic substituent, the considerably steric interaction
between the pinacol phenyls and propargylic group in TS-
II makes the reaction prefer to undergoing via TS-I,[16]
leading to the homoallylic alcohol in the observed
stereochemistry.
1
gel to give the crude products. After H-NMR analysis, the
residue was purified by flash column chromatography
(petroleum ether / DCM = 1:3) on silica gel to afford the
title compound.
Acknowledgements
We are grateful for financial support from NSFC (21602214),
and the China Postdoctoral Science Foundation (No.
2015M580534).
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5
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10.1002/adsc.201700621
Advanced Synthesis & Catalysis
COMMUNICATION
An Enantioselective Multicomponent Carbonyl
Allylation of Aldehydes with Dienes and Alkynyl
Bromides Enabled by Chiral Palladium
Phosphate
Adv. Synth. Catal. Year, Volume, Page – Page
Hong-Cheng Shen, Pu-Sheng Wang, Zhong-Lin
Tao, Zhi-Yong Han, Liu-Zhu Gong*
6
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