10.1002/chem.201805114
Chemistry - A European Journal
FULL PAPER
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In conclusion, we developed a simple synthetic method for the
preparation of vicinally located bis(phosphine) monosulfides by
investigating the addition reactions of diphosphine monosulfides
to alkenes. This reaction readily affords a variety of symmetrical
and unsymmetrical bis(phosphine) monosulfides with excellent
regio- and diastereoselectivities without the need for a catalyst,
base, or additive. Several mechanistic experiments revealed that
the HOMO of diphosphine monosulfide, which, due to the sulfur
atom, is higher than that of the corresponding phosphine oxide,
contributes to an extended absorption-wavelength profile and
improvements in its carbon-radical capturing ability. In view of the
easy accessibility of diphosphine monosulfides and their high
reactivities toward alkenes, we believe this work provides a
powerful tool for the synthesis of symmetrical and unsymmetrical
bis(phosphine) monosulfides as hemilabile ligands for transition-
metal-catalyzed reactions.
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Experimental Section
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The general procedures for the thiophosphinylphosphinations of alkenes
with diphosphine monosulfides were as follows.Diphosphine monosulfide
4 (0.4 mmol) and alkene 2 (0.4 mmol) in degassed dry CH2Cl2 (0.4 mL)
were placed in a sealed Pyrex NMR tube under an argon atmosphere and
the mixture was irradiated with a xenon short arc lamp for 10 hours at room
temperature. After the reaction, the mixture was exposure to air for an hour
and then 30 wt % aqueous hydrogen peroxide solution (0.4 mmol) was
added. BPSO 10 was obtained after isolation by silica gel chromatography
(n-hexane/AcOEt/CHCl3). Further details of the experimental procedures
and characterization data for the new compounds are included in the
supporting information.
Very recently, an addition reaction of diphosphine 1 to styrenes using N-
bromosccinimide and Ir photoredox catalyst was reported. The reaction
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[12] Diphosphine monosulfide 4a decomposed at 40 °C over 3 h to form
Ph2P(S)–P(S)Ph2 (51%) and Ph2P–PPh2 (63%).
Acknowledgements
This research was supported by JSPS KAKENHI Grant Number
16H04138, A.O., H18J15153, Y.S.
Conflict of interest
[13] 1,2-Bis(selenophosphinyl)dodecane (41%), Ph2P–PPh2 (44%), and
Ph2P(Se)–PPh2 (8%) were generated after the reaction. The bis-adduct
9aa was not detected by 1H NMR spectroscopy.
The authors declare no conflict of interest.
[14] Diphosphine monoselenide 5 (0.4 mmol) was dissolved in CD2Cl2 (0.4
mL) and exposed to photoirradiation condition for 20 h. Most of the 5
remained unchanged, but a small amount of 5 transformed into Ph2P–
Se–PPh2 (11%).
Keywords: Phosphanes • Phosphorylation • Radical reactions •
Regioselectivity • Phosphane ligands
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[17] Diphosphine monosulfide 4a (0.4 mmol) was dissolved in CD2Cl2 (0.4
mL) and exposed to photoirradiation condition for 20 h. Most of the 4a
remained unchanged, but
a small amount of 4a decomposed to
[3]
[4]
diphosphine 1 (6%), Ph2P(S)–S–PPh2 (5%), and Ph2P(S) –P(S)Ph2 (1%).
This result shows that the homolytic cleavage of the P(S)–P single bond
in 4a under photoirradiation condition is highly reversible.
[18] When the mixture of diphosphine monosulfide 4a (0.4 mmol) and 4e ((p-
tol)2P(S)–P(p-tol)2, 0.4 mmol, Table 3) dissolvied in CD2Cl2 (0.6 mL) was
irradiated with
a xenon lamp (500 W) for 4 h, four diphosphine
monosulfides and other compounds were observed by 31P NMR
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