Nickel(II)-magnesium-catalyzed cross-coupling of 1,1-dibromo-1-alkenes with diphenylphosphine oxide: One-pot synthesis of (E)-1-alkenylphosphine oxides or bisphosphine oxides

Article abstract of DOI:10.1002/adsc.201200853

A novel nickel(II)-magnesium-mediated cross-coupling of diphenylphosphine oxide with a variety of 1,1-dibromo-1-alkenes has been developed, which provides a powerful and general methodology for the stereoselective synthesis of various (E)-1-alkenylphosphine oxides or bisphosphine oxides, with operational simplicity of the procedure, good to high yields and broad substrate applicability. Mechanistic studies reveal that the reaction might involve a Hirao reduction, cross-coupling and Michael addition. Copyright

Full text of DOI:10.1002/adsc.201200853

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DOI: 10.1002/adsc.201200853
Nickel(II)-Magnesium-Catalyzed Cross-Coupling of 1,1-Dibromo-
1-alkenes with Diphenylphosphine Oxide: One-Pot Synthesis of
(E)-1-Alkenylphosphine Oxides or Bisphosphine Oxides
Liu Liu,a Yulei Wang,a Zhiping Zeng,c Pengxiang Xu,a Yuxing Gao,a,*
Yingwu Yin,b,* and Yufen Zhaoa
a
Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and
Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, Peopleꢀs Republic of China
Fax : (+86)-592-218-5780; e-mail: gaoxingchem@xmu.edu.cn
Department of Chemical and Biological Engineering, College of Chemistry and Chemical Engineering, Xiamen
b
University, Xiamen 361005, Fujian, Peopleꢀs Republic of China
Fax : (+86)-592-218-6198; e-mail: ywyin@xmu.edu.cn
School of Pharmaceutical Science, Xiamen University, Xiamen 361005, Peopleꢀs Republic of China
c
Received: September 24, 2012; Revised: November 28, 2012; Published online: February 22, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200853.
Abstract: A novel nickel(II)-magnesium-mediated
cross-coupling of diphenylphosphine oxide with
a variety of 1,1-dibromo-1-alkenes has been devel-
oped, which provides a powerful and general meth-
odology for the stereoselective synthesis of various
(E)-1-alkenylphosphine oxides or bisphosphine
oxides, with operational simplicity of the procedure,
good to high yields and broad substrate applicabili-
ty. Mechanistic studies reveal that the reaction
might involve a Hirao reduction, cross-coupling and
Michael addition.
phine oxides are used as organoextractions in hydro-
metallurgy,[6] and are key intermediates for the prepa-
ration of various valuable phosphine ligands[7] in ho-
mogeneous catalysis, organocatalysts for the allylation
of N-acylhydrazones[8] and stereoselective direct aldol
reactions of trifluoroethyl thioestesters.[9]
Recently, a few transition metal-catalyzed methods
for the preparation of alkenylphosphine oxides have
continuously emerged including the Pd-catalyzed
cross-coupling of alkenyl halides with phosphine
oxides,[10] olefin cross-metathesis,[11] Cu-catalyzed de-
carboxylative coupling,[12] cleavage of silylepoxides[13]
or stannyloxiranes[14] with lithium diphenylphosphide,
hydrophosphination of terminal alkynes with diphos-
phines and hydrosilanes in the presence of oxygen,[15]
Rh-catalyzed reaction of 1-alkynylphosphines with
water,[16] in situ reactions of functionalized mono-
Keywords: (E)-1-alkenylphosphine oxides; bisphos-
phine oxides; 1,1-dibromo-1-alkenes; DFT calcula-
tions; nickel(II)-magnesium catalysis
AHCTUNGTRENNUNG
Transition metal-catalyzed carbon-phosphorus bond
ACHTUNGTRENNUNG
formation by cross-coupling reactions has attracted several methods such as the Pd-[18f,19] or Rh-cata-
increasing attention in the last two decades due to its lyzed[20] double hydrophosphinylation of alkynes, sub-
wide applicability in biological, pharmaceutical, mate- stitution reactions of 1,2-dichloride complex,[21]
rial and catalytic sciences.[1] Alkenylphosphine oxides double nucleophilic addition of secondary phosphine
and bisphosphine oxides are important classes of oxides to methylacetylene,[22] Kolbe electrolytic cou-
phosphorus-containing, extremely valuable com- pling reactions of phosphinoyl-acetic or propanoic
pounds in organic chemistry. For example, alkenyl- acids[23] and catalytic olefin cross- or homo-metathe-
phosphine oxides are endowed with a wide-range of sis.[11,24] However, these traditional procedures suffer
biological activities,[2] outstanding flame-retardant from relatively strict reaction conditions, low selectivi-
properties[3] and eminent metal-complexing abilities ty, poor substrate scope or unsatisfactory yield, and
as ligands.[4] Furthermore, they can serve as useful there is still a strong need for developing more con-
precursors in the synthesis of a variety of synthetically venient and efficient approaches to alkenylphosphine
elaborated bifunctional adducts by the ready addtion oxides and bisphosphine oxides. It is extremely worth-
of several nucleophiles to the double bond.[5] Bisphos- while to develop highly efficient methods to prepare
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alke
ACHTUNGTRENNUNGnylphosphine oxides and bisphosphine oxides reaction: KOH, 0%; Cs2CO3, 20%; K2CO3, 38%; and
from 1,1-dibromo-1-alkenes as starting materials be- Et3N, 0%.
cause 1,1-dibromo-1-alkenes are important and readi-
Under the optimized conditions shown in footnote
ly available building blocks,[25] which can be conven- [a] of Table 1, we next surveyed the cross-coupling of
iently prepared by Corey–Fuchs reaction.[26] Herein various substituted 1,1-dibromo-1-alkenes with diphe-
we disclose a novel methodology for the highly effi- nylphosphine oxide to understand the scope of the re-
cient preparation of stereoselective (E)-1-alkenyl- action. As demonstrated in Table 1, the corresponding
phosphine oxides or bisphosphine oxides from readily coupling products were produced in moderate to
available 1,1-dibromo-1-alkenes and diphenylphos- good yields with high stereoselectivity in favor of the
phine oxide through Ni(II)-Mg-mediated cross-cou- (E)-isomer. When a variety of electron-withdrawing
pling with the advantages of operational simplicity of or electron-donating groups was introduced on the
the procedure, good to high yields and broad sub- phenyl ring of the 1,1-dibromo-1-alkenes, the results
strate applicability (Scheme 1). To the best of our illustrated that electronic effects and steric hindrance
knowledge, this method is the first example of are not operative in this coupling reaction (Table 1,
a Ni(II)-Mg-mediated cross-coupling of 1,1-dibromo- entries 2–11, 19). Notably, heterocycle-substituted 1,1-
1-alkenes with diphenylphosphine oxide leading to dibromo-1-alkenes were also found to be suitable re-
(E)-1-alkenylphosphine oxides or bisphosphine action partners, and the corresponding coupling prod-
oxides.
ucts were obtained in good yields (Table 1, entries 12–
Initially, we chose 2,2-dibromovinylbenzene (1a) 14). However, aliphatic 1,1-dibromo-1-alkenes gave
and Ph2P(O)H as the model substrates to optimize lower yields than aromatic ones (Table 1, entries 17
the catalysis conditions. When a mixture of 1a and 18), for example, the coupling of diphenylphos-
(0.30 mmol),
Ph2P(O)H
(0.66 mmol),
NiCl2 phine oxide with 2,2-dibromovinylbenzene (1a) af-
(0.03 mmol), 2,2’-bipyridine (bpy, 0.06 mmol), K3PO4 forded an 88% isolated yield, whereas 1,1-dibromo-
(1.80 mmol) in THF was heated at 708C overnight non-1-ene (1q) showed lower reactivity under the
under dry argon, only a trace amount of product was same conditions and provided a 66% yield. 1,1-Dibro-
obtained. However, when Zn or Mg (0.30 mmol) was moprop-1-en-2-yl)benzene (1s) could also be used as
added to the reaction system, the reaction yields were the substrate to give the desired product in 90% yield
greatly improved and alkenylphosphine oxide 2a was (entry 19). Gratifyingly, the present catalytic reaction
formed in 78% or 84% yield with high stereoselectiv- was also successfully applied to the coupling of 1,4-
ity (E/Z=92/8, 92/8), respectively. A screening of the bis(2,2-dibromovinyl)benzene (1t) with diphenylphos-
catalysts showed that Ni(II) salts, especially NiBr2, phine oxide and predominantly furnished the (E)-
was found to be the most effective catalyst to gener- isomer in 70% yield (entry 20). In regard to the reac-
ate the desired product 2a. Catalysts (10 mol%) and tant, in addition to diphenylphosphine oxide, H-phos-
corresponding yields of 2a were as follows: NiBr2, phonate diesters could also be used as the substrates,
88%; Ni
82%. Under similar reaction conditions, other metal yield. For example, the coupling of diethyl and diiso-
salts, such as AgI, CuBr and FeCl2, did not or only propyl phosphonate with 1,1-dibromo-1-alkenes
ACHTUNGTRENNUNG(OAc)2, 77%; NiACHTUNRTEGN(GNUN acac)2, 80% and NiACHTNUGTREN(NUNG NO3)2, generating the corresponding products in moderate
ACHTUNGTRENNUNG
sluggishly promoted this reaction. No obvious change under similar reaction conditions could proceed
in yield was observed when the loading of Mg was in- smoothly, giving 70% and 74% yield and high stereo-
creased to 2.0 equiv. Ligand screening showed that selectivity for E/Z=94/6 and 94/6 isomers, respective-
bpy was the best choice. The type of solvent was vital ly (for details see the Supporting Information). Obvi-
to the present catalytic reaction. Besides THF (88%) ously, this approach affords a strong tool for the prep-
and DMF (66%), other solvents including toluene, di- aration of the valuable P-alkenylated motifs.
oxane, CH2Cl2 and MeCN, produced only a trace
amount of product 2a. Bases also highly affected this in the synthesis of enantiomerically pure P-chiral alk-
enylphosphinate 3b[27] from optically pure H-phosphi-
It is noticeable that this procotol could also be used
AHCTUNGTRENNUNG
Scheme 1. Ni(II)-Mg-catalyzed one-pot preparation of (E)-1-alkenylphosphine oxides or bisphosphine oxides.
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Adv. Synth. Catal. 2013, 355, 659 – 666

Nickel(II)-Magnesium-Catalyzed Cross-Coupling of 1,1-Dibromo-1-alkenes with Diphenylphosphine Oxide
Table 1. Ni(II)-Mg-catalyzed one-pot preparation of (E)-1-alkenyl-phosphine oxides.[a]
[a]
Reaction conditions: 1 (0.50 mmol), Ph2P(O)H (1.10 mmol), NiBr2 (0.05 mmol), Mg (0.5 mmol), bpy (0.10 mmol), K3PO4
(3.0 mmol), THF (2.5 mL), 708C, 3 h.
[b]
Isolated yield.
[c]
[d]
1
Defined by in situ H NMR or 31P NMR.
The amount of other reagents doubled except for 1, 5 h.
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Liu Liu et al.
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nate 3a[28] with retention of configuration at the phos- high selectivity for the (E)-isomer (94/6, entry 2).
phorus atom (Scheme 2). However, under similar reaction conditions, H-phos-
More interestingly, the bisphosphine oxides were phonate diester as substrate did not afford the desired
produced through increasing the amount of bisphosphonate product.
Ph2P(O)H to 3.2 equiv. (Table 2). This one-pot reac-
To gain more insight into the reaction mechanism,
the catalytic pathway has been investigated in detail
using a combination of experiments and density func-
tional theory (DFT) calculations. When substrate 1a
was treated with 3 equiv. of Ph2P(O)H and 6 equiv. of
K3PO4 in the absence of NiBr2/Mg catalyst, only 2-
bromovinylbenzene (E/Z=92/8) was produced after
stirring at 708C in THF for 10 h (Scheme 3), clearly
demonstrating that the configuration of diphenyl-
AHCTUNGTREG(NNUN styryl)phosphine oxide (2a) (E/Z=92/8) was deter-
mined by that of the product of a Hirao-type reduc-
tion,[29] and the Ni(II)-Mg catalyst played the key role
in the next coupling step. The Michael addition of
diphenylACTHNUTRGNEUG(N styryl)phosphine oxide (2a) with 1.5 equiv.
of Ph2P(O)H and 5 equiv. of K3PO4 without a metal
catalyst was investigated and the double-hydrophos-
phinylated product (4a) was obtained in excellent
yield (96%). These results illustrated that the cou-
pling step was metal-catalyzed, and the addition step
was promoted by the base.[30]
Scheme 2. Ni(II)-Mg-catalyzed cross-coupling of 1a with op-
tically pure H-phosphinate 3a.
tion performed quite well for all the substrates exam-
Based on the nickel- and palladium-catalyzed cross-
ined, and the desired bisphosphine oxides were ob- coupling reaction mechanisms,[31] we proposed a possi-
tained in good to excellent yields. The results indicat- ble mechanism of the Ni(II)-Mg catalyzed cross-cou-
ed that aromatic 1,1-dibromo-1-alkenes showed better pling step. The active catalytic species IN0 was pro-
reactivity than aliphatic ones (Table 2, entries 1 and duced from the catalyst precursor NiBr2 in the pres-
3). It is noteworthy that cinnamaldehyde-derived 1,1- ence of reducing magnesium powder and bpy. The ap-
dibromoalkenes (1u) underwent the reaction to pro- proach of (E)-(2-bromovinyl)benzene toward IN0
duce the 1,4-addition product 4b with good yield and leads to the formation of the h2 complex IN1. Oxida-
Table 2. Ni(II)-Mg-catalyzed one-pot synthesis of bisphosphine oxides.[a]
[a]
Reaction conditions: 1 (0.50 mmol), Ph2P(O)H (1.60 mmol), NiBr2 (0.05 mmol), Mg (0.5 mmol), bpy (0.10 mmol), K3PO4
(3.0 mmol), THF (3.0 mL), 708C.
[b]
Isolated yield.
E/Z was defined by in situ H NMR.
[c]
[d]
1
The amount of other reagents doubled except for 1, 5 h.
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Nickel(II)-Magnesium-Catalyzed Cross-Coupling of 1,1-Dibromo-1-alkenes with Diphenylphosphine Oxide
Scheme 3. Mechanistic studies.
tive addition of IN1 proceeds through a three-mem- perimental observation that the Ni-Mg-catalyzed re-
bered-ring transition state TS1. The free energy of action was carried out at 60–708C.[32] The structure of
TS1 is +14.4 kcalmolÀ1 higher than that of IN1, indi- the corresponding transition state is shown in
cating that oxidative addition is a facile step. The im- Scheme 3 (hydrogens are not shown for clarity). It is
mediate product of oxidative addition, a four-coordi- interesting to note that the plotted highest occupied
nated Ni(II) complex IN2, is more stable than IN0 by molecular orbital (HOMO) shows bonding interaction
À35.4 kcalmolÀ1. Subsequent ligand exchange with di- between the d-orbital of Ni and p-orbital of P and Ni-
phenylphosphinite generates a Ni(II) species IN3 with bonded C atoms (Figure 1). The contribution from
a negative energy of À9.9 kcalmolÀ1. From IN3 other carbons on the phenyl ring of 1,1-dibromo-1-
a three-membered ring transition state TS2 is indenti- alkACTHNUGRTENUNGenes to the HOMO is very small, in accord with
fied for the reductive elimination. The overall barrier the experimental results that both electron-withdraw-
from IN3 to TS2 is computed to be 25.6 kcalmolÀ1. ing and electron-donating groups on the aromatic 1,1-
À
The calculated results indicate that the first two steps dibromo-1-alkenes have no evident effect on the C P
are barrierless processes, and the rate-determining bond formation.
À
step is the C P bond formation, in line with the ex-
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For 2t: the amount of other reagents was doubled except
for 1t.
For 3b: 3a (1.10 mmol) replaced Ph2P(O)H, at 608C.
General Procedure for the Synthesis of 4a–4d
For 4a–4c: an oven-dried Schlenk tube containing 1,1-dibro-
mo-1-alkene (0.50 mmol), Ph2P(O)H (1.60 mmol), NiBr2
(0.05 mmol), Mg (0.50 mmol), bpy (0.10 mmol) and K3PO4
(3.0 mmol) was evacuated and purged with argon three
times. Freshly distilled THF (3.0 mL) was added at room
temperature, and then the resulting mixture was stirred at
708C for the indicated time. The crude product was purified
by the procedure described above.
For 4d: the amount of other reagents doubled except 1v.
Computational Methods
All the calculations were performed with the Gaussian 03
programs.[33] The gas phase geometries of all compounds
were optimized without any constraint by the density func-
tional theory (DFT) method B3LYP. The 6-31+G(d) basis
set was used for C, H, N, O, P. Polarization functions were
added for Br (xd =0.428) and Ni (xf =3.130) to the standard
LANL2DZ basis set.[34] Frequency analysis was performed
after optimization to verify the minima and transition states.
Intrinsic reaction coordinate (IRC) calculations of the tran-
sition states were performed to confirm that the transition
states were located on the real saddle points of the reaction
potential energy surfaces. For compounds that had multiple
conformations, efforts were made to find the lowest-energy
conformation by comparing the structures optimized from
different starting geometries. Single-point electronic ener-
gies were calculated by using the B3LYP method. The
Figure 1. The HOMO (isovalue=0.04) of the located TS2
by DFT calculations.
In summary, we have successfully developed
a simple and highly efficient method for the synthesis
of (E)-1-alkenylphosphine oxides or bisphosphine
oxides through direct coupling of readily available
1,1-dibromo-1-alkenes with diphenylphosphine oxide
under mild reaction conditions. This cross-coupling is
firstly performed under catalysis of commercially
available and inexpensive Ni(II)-Mg catalyst system,
and various valuable products can be conveniently
obtained in a one-pot process. Preliminary mechanis-
tic studies indicate that this reaction might involve
a Hirao-type reduction, Ni(II)-Mg-catalyzed cross-
coupling and Michael addition. Further mechanistic
details and synthetic applications are currently under-
way.
SDD[35] basis set was used for Ni and 6-311+G
ACTHUNTGRENNG(U 2d, p) was
used for other atoms. The Gibbs free energy correction
from frequency calculation was added to the single-point
energy to obtain the Gibbs free energy. To calculate the sol-
vation energies, the IEF-PCM method with the UA0 radii
was used. The gas-phase geometry was used for all of the so-
lution phase calculations. The solvation free energy was
added to the gas-phase free energy to obtain the Gibbs free
energy in solution. All the solution-phase free energies re-
ported in the paper correspond to the reference state of
1 mol/L, 298 K.
Acknowledgements
Experimental Section
We acknowledge financial support from the Chinese National
Natural Science Foundation (21202135, 21075103, 21232005),
the National Basic Research Program of China
(2012CB821600), and TJAB-2009-023.
General Procedure for the Synthesis of 2a–2t and 3b
For 2a–2s: an oven-dried Schlenk tube containing NiBr2
(0.05 mmol), Mg (0.50 mmol), bpy (0.10 mmol), Ph2P(O)H
(2a–2s) (1.10 mmol), K3PO4 (3.0 mmol), and 1,1-dibromo-1-
alkene (0.50 mmol) was evacuated and purged with argon
three times. Freshly distilled THF (2.5 mL) was added at References
room temperature, and then the resulting mixture was
stirred at 708C for the indicated time. After completion of
the reaction, the reaction mixture was cooled to room tem-
perature and the solvent was removed under reduced pres-
sure. The residue was purified by column chromatography
(silica gel, petroleum ether-EtOAc or CH2Cl2-CH3OH).
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ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 659 – 666