Visible-Light-Promoted Regio- and Stereoselective Oxyalkenyl-ation of Phosphinyl Allenes

Article abstract of DOI:10.1002/adsc.202000214

A highly regio- and stereoselective oxyalkenylation of phosphinyl allenes is revealed for the first time. This protocol, merging visible light photoredox and palladium catalysis, provides a direct approach to conjugated tertiary allylic alcohol derivatives with broad functional group tolerance in moderate to excellent yields. Mechanistic studies suggest that, although two possible pathways exist in the transformation, radical oxyalkenylation promoted by visible light photoredox takes over the major pathway. (Figure presented.).

Full text of DOI:10.1002/adsc.202000214

Title: Visible-Light-Promoted Regio- and Stereoselective
Oxyalkenylation of Phosphinyl Allenes
Authors: Xue Sun, Teng Liu, Yan-Tong Yang, Yue-Jie Gu, Yu-Wei Liu,
Yi-Gang Ji, Kai Luo, and Lei Wu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000214
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Visible-Light-Promoted Regio- and Stereoselective Oxyalkenyl-
ation of Phosphinyl Allenes
Xue Sun,a Teng Liu,b Yan-Tong Yang,a Yue-Jie Gu,a Yu-Wei Liu,a Yi-Gang Ji,c Kai
Luo,a and Lei Wu a,*
a
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural
University, Nanjing 210095, P. R. China.
[Tel/Fax: +86-25-84395351; E-mail: rickywu@njau.edu.cn]
b
College of Chemistry and Material Science, Shandong Agricultural University, Taian, Shandong 271018, P. R. China.
Jiangsu Key Laboratory of Biofunctional Molecules, Department of Life Sciences and Chemistry, Jiangsu Second
c
Normal University, Nanjing 210013, P. R. China.
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.202######.((Please
delete if not appropriate))
Abstract. A highly regio- and stereoselective oxyalkenylation of phosphinyl allenes is revealed for the first time. This
protocol, merging visible light photoredox and palladium catalysis, provides a direct approach to conjugated tertiary
allylic alcohol derivatives with broad functional group tolerance in moderate to excellent yields. Mechanistic studies
suggest that, although two possible pathways exist in the transformation, radical oxyalkenylation promoted by visible
light photoredox takes over the major pathway.
Keywords: Phosphinyl Allenes, Oxyalkenylation, Visible Light, Palladium Catalysis, Conjugated Tertiary Allylic
Alcohol derivatives.
contributed diverse intermolecular three-component
protocols (Scheme 1a), named as nitro-oxoamination,
Introduction
oxyarylation, trifluoromethylazidation, trifluoro-
methylthiocyanation, oxysulfonylation, oxytrifluoro-
methylation, and so on.
Allenes are attractive molecules possessing two
cumulative carbon-carbon double bonds, which have
been served as versatile synthons for constructing
bioactive synthetic compounds, naturally-occurring
products, as well as optoelectric materials.[1] For the
past several decades, various difunctionalizations of
allenes have been established as powerful and step-
economical approaches to enrich molecular
complexity.[2] Apart from well-known electrophilic
addition[2a,b] and transition-metal catalysis,[2c,d]
radical-based difunctionalization of allenes represents
an emerging research topic within recent years, most
often furnishing value-added olefins.[3] For an elegant
study, in 2012, Ma’s group developed a novel
intramolecular radical addition/cyclization reactions
of allene-enes to afford perfluoroiodinated products.[4]
Later on, leading scientists such as Ma,[5] Kanai,[6]
Liu,[7] Lei,[8] Akita,[9] as well as others[10] have
Although much progress has been made in this
field, challenges still remain as follows: (1) Due to
difficulties in controlling the regio- and stereo-
selectivity, only a few strategies dealed with electron-
deficient and/or multi-substituted allenes. For
example, in Lei’s work,[8] ester substitutions
completely altered the oxysulfonylation pathway to
produce terminal alkenes exclusively. Non-terminal
di- and tri-substituted allenes bred regioselective
adducts but with much lower stereoselectivities.[6],[9]
(2) Despite that oxyalkenylation has been reported as
a highly efficient protocol to modify alkenes,[11] to the
best of our knowledge, oxyalkenylation of allenes has
never been documented. This strategy will provide a
direct approach to access conjugated tertiary allylic
alcohol derivatives, and both the diene and tertiary
1
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
allylic alcohol moieties can be further used as pivotal
synthons.[12] However, construction of linear
chemistry,[14] herein, we disclose a highly regio- and
stereoselective oxyalkenylation of phosphinyl allenes
enabled by merging palladium catalysis and
photocatalysis (Scheme 1b).
conjugated π-systems also presents
a
unique
challenge, where each C=C bond needs to be
produced in regio- and stereoselective manner.[13] As
our continuing interest in radical and allene
Scheme 1. (a) Previous Reports on Radical Difunctionalization of Allenes; and (b) This Work.
free condition, where all the substrates remained
intact (entries 10-12). Systematical screenings of the
conditions were further performed on various
solvents and additives. As comparisons, reactions in
aqueous THF or DMF conducted better than that of
anhydrous solvent (entries 13-15). A successful
attempt in entry 16 revealed that the reaction gave the
product 3aa in 95% yield under conditions with iron
phthalocyanine (FePc) as a photocatalyst, 1-hydroxy-
2-oxa-1-ioda(III) indan-3-one (BI-OH) and trifluoro-
acetic acid as additives, and DMSO/H2O as solvents.
It’s worthy to mention that the utility of appropriate
additives and visible-light source is crucial to
enhance the efficiency (entries 17-25). Because that
most of the metallated phthalocyanines show strong
absorption bands in the wavelength region from 600
to 700 nm,[15] red LED irradiation was found to be the
most efficient light source. Thus, a highly regio- and
stereoselective oxyalkenylation of phosphinyl allenes
catalyzed by palladium complex and FePc was
achieved to give conjugated tertiary allylic alcohol
derivatives.
Results and Discussion
With tert-butyl acrylate (1a) and tri-substituted
phosphinyl allene (2a) as the model substrates, we
discovered that, in the absence of photosensitizer, a
palladium catalyst itself could give 9% yield of
oxyalkenylation adduct (3aa, entry 1), with two
double bonds determined as (E)- and (Z)-
configurations, respectively. As shown in Table 1,
photosensitizer, palladium precursor, solvent and
additive played crucial roles in furnishing the final
product. A wide range of photocatalysts, including
eosin Y, eosin B, Ru(bpy)2Cl2, and metal
phthalocyanine complexes of zinc or copper (ZnPc,
CuPc), was found to be less effective, with yields
isolated less than 50% (entries 2-6). Phthalocyanine
itself might coordinate with palladium salt, thus
forming PdPc to enable the catalytic cycle as well
(entry 7). Palladium acetate and palladium dichloride
independently enabled the oxyalkenylation to some
extent (entries 8,9); however, the presence of phos-
phine ligands gave identical results with a palladium-
Table 1. Optimization of Reaction Conditions[a]
2
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
additive/solvent/light source
entry
1
photocatalyst/catalyst
yield (3aa,%)[b]
-/(CF3COO)2Pd
BI-OH+TFA/DMSO:H2O/54 W red LEDs
9
2
eosin Y/(CF3COO)2Pd
eosin B/(CF3COO)2Pd
Ru(bpy)2Cl2/(CF3COO)2Pd
ZnPc/(CF3COO)2Pd
CuPc/(CF3COO)2Pd
Phthalocyanine/(CF3COO)2Pd
FePc/Pd(OAc)2
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
32
34
3
4
31
5
48
6
22
7
66
8
64
9
FePc/PdCl2
24
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
FePc/Pd(PPh3)4
N.R.
N.R.
N.R.
FePc/Pd(PPh3)2Cl2
FePc/-
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd s
FePc/(CF3COO)2Pd
FePc/(CF3COO)2Pd
BI-OH+TFA/anhydrous DMSO/54 W red LEDs
BI-OH+TFA/THF:H2O/54 W red LEDs
BI-OH+TFA/DMF:H2O/54 W red LEDs
BI-OH+TFA/DMSO:H2O/54 W red LEDs
BI-OH/DMSO:H2O/54 W red LEDs
TFA/DMSO:H2O/54 W red LEDs
trace
40
30
95
70
55
TBHP/DMSO:H2O/54 W red LEDs
DTBP/DMSO:H2O/54 W red LEDs
H2O2/DMSO:H2O/54 W red LEDs
trace
25
17
BI-OH+TFA/DMSO:H2O/15 W red LEDs
BI-OH+TFA/DMSO:H2O/white LEDs
BI-OH+TFA/DMSO:H2O/green LEDs
BI-OH+TFA/DMSO:H2O/ sunlight
26
29
39
14
[a] Standard conditions: tert-butyl acrylate (1a, 0.4 mmol), phosphinyl allene (2a, 0.2 mmol), iron phthalocyanine (FePc, 5 mol%),
(CF3COO)2Pd (5 mol%), BI-OH (0.2 mmol), trifluoroacetic acid (TFA, 0.4 mmol), DMSO:H2O (2 mL, v/v=1:1), irradiated by 54
W Red LEDs under air at 25 oC for 48 hours;
[b] Isolated yield, N.R. = no reaction.
were obtained as well in yields ranging from 68% to
After establishing the optimized reaction
82% (3aj-3al), with an exception for compound 3ai.
conditions, we turned our attention to investigate the
To be noted, low yield of 3ai might be ascribed to
scope of phosphinyl allenes by employing tert-butyl
steric hindrance since no ring-opening by-product
acrylate 1a as the substrate, as illustrated in Scheme
was detected and most of the substrate 2i were left
2. Generally, phosphinyl allenes bearing alkyl, cyclic
unreacted. The phenomena also appeared while
and heterocyclic substitutions afforded the
expanding the substituent to aromatics. Allene with
corresponding adducts in moderate to excellent yields.
an endmost p-methoxy-benzyl (PMB) group
Substrates with acyclic aliphatic substitutions
underwent oxyalkenylation rather smoothly to deliver
including methyl, ethyl, n-propyl, n-butyl, i-butyl, i-
73% yield of 3am; unfortunately, phenyl group (2n)
pentyl, and n-hexyl (2a-2h) performed smoothly in
gave only lower yield of 32% even after attempted
the process, albeit long chain substituents partly
screenings. To our delight, p-tosyl and ester derivated
impaired the reaction efficiency probably due to
allenes could also be converted into conjugated
blocking
effect.
Moreover,
the
correct
allylic alcohol derivatives (3′ and 3″), though the
reaction efficiency decreased considerably.
stereochemistry of molecule 3ab was verified by X-
ray crystallography (CCDC 1963373). Substrates
bearing distal alicyclic and heterocyclic groups were
amenable to the system, and the desired products
3
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
Scheme 2. Substrates Scope on Phosphinyl Allenes.
TFA, but higher loadings of catalysts were necessary.
Thereafter, a variety of styrene derivatives were
applied, the corresponding hydroxyl alkenyl adducts
were furnished smoothly. When changing the
substituents of olefins, it was concluded that both
electron-donating (such as methyl and methoxy, 1g-
1j) and electron withdrawing groups (such as F and
Cl, 1k-1n) on the phenyl ring were well tolerated,
giving the corresponding products in moderate yields.
In general, substrates bearing substitutions on meta-
positions or ortho-positions also proceeded efficiently
albeit affording comparatively lower yields compared
With the aim of broadening the scope of this
protocol, thereafter, general applicability of other
olefins was investigated (Scheme 3). In addition to
tert-butyl acrylate, several acrylates were found to be
applicable to the system with good yields ranging
from 68% to 76% (3bc-3dc, 3eb). However, when it
came to styrene derivatives, the yields dramatically
decreased to less than 20% owing to the rapid dimeri-
zation of styrene derivatives upon treatment with
trifluoroacetic acid.[16] To our delight, the
transformation performed smoothly without adding
4
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
with para-positions in yields ranged from 40% to
55% (compounds 3gb-3ib, and 3lb-3nb). It is worthy
to mention that reactive bromide group survived
under the palladium catalysis conditions and
transformed into 3ob in 60% yield. And nitro group,
a well-known notorious radical inhibiting unit, did
not demolish the reaction process, producing 3pb
with 60% yield. Non-terminal acrylates and styrene
derivatives, unactivated olefins, and terminal alkynes
were not suitable substrates for this protocol.
Scheme 3. Substrates Scope on Olefins[a],[b]
[a] Condition for 1b-1e: standard conditions; Condition for 1f-1p: styrene derivative (1, 1 mmol), phosphinyl allene (2, 0.2 mmol),
iron phthalocyanine (FePc, 10 mol%), (CF3COO)2Pd (10 mol%), BI-OH (0.2 mmol), DMSO:H2O (2 mL, v/v=1:1), irradiated by
54 W Red LEDs under air at 25 oC for 48 hours.
[b] Isolated yield.
may proceed with molecular water as a source of the
In order to investigate the reaction mechanism,
several control experiments and intermediate capture
experiments were designed and performed (Scheme
4). With the addition of tosylated diallylamine under
standard conditions, an alkenyl radical intermediate
(4) was captured and the resulting adducts were
detected by HR-MS (eq a, see details in the
Supporting Information). Notably, in the absence of
palladium catalyst, the intermediate 4 would not be
produced. Radical inhibition experiments, as
described in eq b, strongly suggested that a non-
radical pathway might exist since large amounts of
scavengers (TEMPO or BHT) and reaction in dark
did not entirely cease the process, affording product
3ac in similar yields around 20%. The isolation of
certain product under oxygen-free condition (N2
atmosphere) indicated that the non-radical pathway
hydroxyl group. Taking into account that metal
phthalocyanine complexes under irradiation are well-
known to produce singlet oxygen,[17] we con-ducted a
trap experiment with 1,3-diphenyl-isobenzofuran and
an EPR study. Both results confirmed the existence of
singlet oxygen, moreover, palladium catalyst was
proven to be irrelative with generating singlet oxygen
(eq c). Although singlet oxygen has been well-
documented as highly active species in attacking
terminal double bonds to generate peroxide and then
reduced to hydroxyl group,[18] this pathway might not
occur under current circumstances, otherwise, the
intermediate 4 should not be detected and all the
reactions performed smoothly under palladium-free
conditions. Based on the above experimental
observations, palladium complex might play dual
roles in the step of producing hydroxyl radical and
5
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
serving as metal catalyst in the non-radical pathway.
To determine the origin of the oxygen atom, 18O-
labeling experiments were conducted with isotopic
H2O and oxygen, respectively (eq d). Interestingly,
18O-labelled product (3ah-18O) was detected in both
reactions, which could be ascribed to rapid atom
exchange between the hydroxyl radical and water
molecules. In other words, the oxygen atom derived
from both molecular oxygen and water.
Scheme 4. Mechanism Studies.
other hand, the photocatalyst, iron phthalocyanine
(denoted as FePc), is activated by visible light to give
an excited state FePc*. An energy transfer occurs
between FePc* and oxygen to form a singlet oxygen
species and close the cycle.[21] The singlet oxygen
abstracts an electron from phosphinyl allene 2 to
produce a radical cation [A] and an oxygen radical
anion.[14d] Subsequently, the oxygen radical anion
reacts with in-situ generated hydrogen peroxide,
namely Haber-Weiss reaction,[22] yielding singlet
oxygen, hydroxyl anion and hydroxyl radical. The
resulting hydroxyl radical attacks the allenic terminus
to furnish the key alkenyl radical intermediate 4,
which then adds to substrate 1 delivering intermediate
Though the overall mechanism of oxy-
alkenylation are not very clear at present, we propose
a possible catalytic cycle on the major pathway
(Scheme 5), according to experimental facts, our
previous work[14d] and literature reports.[19] On one
hand, palladium (II) complex catalyzes an oxidative
coupling of terminal alkene 1 and water, followed by
β-hydride elimination to produce Pd0 catalyst
(Wacker-type oxidation).[19c],[20] Subsequent aerobic
oxidation of Pd0 leads to the formation of a peroxo-
palladium (II) complex. This molecule reacts with
Brønsted acid to release hydrogen peroxide and
regenerate the palladium (II) catalyst.[19a,b] On the
6
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
[B]. Sequential radical oxidation of [B] and proton
elimination finalizes the reaction process. The
additives of BI-OH and trifluoroacetic acid are
believed to enhancing the efficiency of generated
hydroxyl radical thus accelerating the reaction
rate.[14d]
Scheme 5. Proposed Mechanism.
(eq b), the conjugated allylic alcohols dehydrated to
form new series of stereoselective phosphinyl
[3]dendralenes, which provides a novel strategy to
build multi-substituted dendralenes.[14a],[14c],[23]
The protocol could be scaled up to at least a gram-
scale, furnishing the corresponding product (3ac) in
40% yield (Scheme 6, eq a). Additionally, upon the
treatment of catalytic amount of aluminium chloride
Scheme 6. Gram-scale Synthesis and Applications.
stereoselective [3]dendralenes. This strategy features
mild reaction conditions, operational simplicity, high
chemoselectivity, and expands the portfolios of
radical and allenes chemistry.
Conclusion
In conclusion, we developed an unprecedented
oxyalkenylation of phosphinyl allenes. Merging
visible light photoredox with palladium catalysis, this
protocol offers a straightforward approach to access
conjugated tertiary allylic alcohols with broad
functional group tolerance, as well as high regio- and
stereoselectivity. Synthetic application of the
products could be extended to building
Experimental Section
Typical Procedures for the Visible-Light-Promoted
Oxyalkenylation of Phosphinyl Allenes. To a 10 mL tube
was added tert-butyl acrylate (1a, 0.4 mmol, 51.3 mg),
phosphinyl allene (2a, 0.2 mmol, 56.4 mg), iron
phthalocyanine (FePc, 0.01 mmol, 5.7 mg), (CF3COO)2Pd
(0.01 mmol, 3.3 mg), 1-hydroxy-2-oxa-1-ioda(III) indan-3-
7
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10.1002/adsc.202000214
Advanced Synthesis & Catalysis
one (BI-OH, 0.2 mmol, 52.8 mg), trifuoroacetic acid (TFA,
0.4 mmol, 45.6 mg), DMSO/H2O (2 mL, v/v=1:1),
irradiated by 54 W Red LEDs under air at 25 C for 48
15333; b) Y. Tang, Q. Yu, S. Ma, Org. Chem. Front.
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o
hours. The resulting mixture was diluted with ethyl acetate
and washed with brine. The combined organic layer was
collected and concentrated. The resulting residue was
purified by column chromatography (eluent: 1:2 (v/v) of
ethyl acetate/petroleum ether) to afford product 3aa (80.7
mg, 95% yield) as a white solid, m.p.: 122.7-124.0 °C.
[9] R. Tomita, T. Koike, M. Akita, Chem. Commun. 2017,
53, 4681.
1
TLC (Rf = 0.35, petroleum ether/ethyl acetate = 2:1). H
NMR (400 MHz, CDCl3) δ 7.76-7.69 (m, 4H), 7.55-7.43
(m, 6H), 7.31 (d, J = 14.4 Hz, 1H), 6.30-6.19 (m, 2H), 6.10
(d, J = 15.3 Hz, 1H), 1.81-1.63 (m, 2H), 1.50 (s, 9H), 1.42
(s, 3H), 0.88 (t, J = 7.4 Hz, 3H). 13C NMR (101 MHz,
CDCl3) δ 167.3, 165.2, 144.0 (d, J = 17.3 Hz), 134.2, 133.1,
131.8, 131.8, 131.1 (d, J = 3.5 Hz), 131.0 (d, J = 3.5 Hz),
128.7 (d, J = 7.1 Hz), 128.6 (d, J = 7.1 Hz), 124.7 (d, J =
1.2 Hz), 119.2 (d, J = 100.3 Hz), 81.3, 76.0 (d, J = 4.7 Hz),
34.5, 28.1, 27.9 (d, J = 0.8 Hz), 8.0. 31P NMR (162 MHz,
CDCl3) δ 26.75 (s). HRMS (ESI): ([M+H]+) Calcd for
C25H32O4P+: 427.2033, Found: 427.2029. IR (film) ν 3353,
3053, 2977, 2942, 2921, 2854, 1708, 1627, 1581, 1436,
1366, 1283, 1251, 1159, 964, 926, 843, 814, 748, 694, 619
cm−1. (CCDC number for compound 3ab: 1963373).
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Acknowledgements
This project is supported by the Foundation Research Project
of Jiangsu Province (The Natural Science Foundation, Nos.
BK20180513 and BK20191305), the Fundamental Research
Funds for the Central Universities (NJAU, Grant No.
KYDZ201904), the Qing-Lan Project of Jiangsu Provincial
Department of Education and the “333 High Level Talent
Project” of Jiangsu Province.
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