Phosphorus Chemistry - ACS Publications - American Chemical Society

Chapter 11 Photorearrangements of Allyl Phosphites Wesley G. Bentrude

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Department of Chemistry, University of Utah, Salt Lake City, UT 84112

Photoarrangements of allyl phosphites to the corresponding allylphosphonates are being studied under both direct irradiation and triplet-sensitization conditions. Triplet sensitized processes proceed with a regiochemistry consistent with the intervention of triplet, cyclic, 1,3-biradical phosphoranyl species. Direct irradiation gives phosphonate non-regiospecifically by an undefined process. The incorporation of phosphorus in afive-,six-, or seven-membered ring results in large effects on the apparent relative efficiencies of these processes. Phosphoranyl radical intermediates (Ζ Ρ· e.g., Ζ = alkyl, aryl, ctialkylamino, aryloxy and combinations thereof) have been well-studied over the past two decades. The subject has been reviewed severaltimes(1-8). The formation of these radical intermediates by oxidative addition processes and their subsequent scission processes to yield the products of oxidation and substitution are shown in Scheme I (R = alkyl, benzyl). Somewhat less well characterized are bimolecular processes in which intact phosphoranyl radicals (Ζ Ρ· = a bicyclic or spiro species) are trapped, as illustrated in Scheme I by the reaction with a disulfide (9). 4

4

It occurred to us sometimeago that since electronically excited states of functional groups such as ketone carbonyls and alkenes undergo reactions very similar to those of alkoxy and alkyl radicals, it might be possible to observe reactions of these excited states with three-coordinate phosphorus. Of particular interest would be attack at phosphorus in an intramolecular context as shown conceptually in the equations of Scheme II. In fact we observed the first example of a photorearrangement that may well proceed by such a mechanism over twenty years ago (10). Perhaps one of the most striking examples of carbon radical-like reactivity involving an electronically excited alkene is found in the photoreaction of Scheme 0097H5156/92/0486-0137$06.00/0 © 1992 American Chemical Society Walsh et al.; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1992.

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Scheme I Formation RO* + ΡΖ3 — - RO—ΡΖ3

Unimolecular scission R . + 0=PZ3

(oxidation)


Ζ· + ROPZ2

(substitution)

Bimolecular trapping Z P*^+^RSSR' 4

RSPZ + RS* 4

(S ) H

m (77). The triplet excited state abstracts hydrogen to initiate a sort of Norrish Type Scheme Π

Products II alkene photochemical fragmentation. The singlet, by contrast, undergoes chemistry similar to that of a benzyl cation. Examples of hydrogen abstraction by singlet alkene excited states are also well documented (72,73). Allyl Phosphite Rearrangements One of the photorearrangements studied in this laboratory is the conversion of allyl phosphites to the the corresponding phosphonates (14). Although this rearrangement occurs thermally at 200 °C (72), the photochemical process proceeds readily at room temperature in a matter of hours with light at 254 nm from a Rayonet photoreactor, Scheme IV. Regiochemistry. The process in benzene indeed proceeds with the regiochemistry shown in Scheme V. This result is at least consistent with the presence of the 1,3biradical intermediate of Scheme V. This biradical is formed on attack of the electronically excited alkene functionality according to the concepts of Scheme Π.

Walsh et al.; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1992.

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Photorearrangements of Allyl Phosphites

Scheme III OH H ^ I ^Ph

OH ,Ph .

OH H . I ^Ph . "VU"™

Ph CO 2

Η + CX .Ph


H H .Ο. I . P h

Η P h ^ ^

JO,

p

h

°T

+

PhX

M

^

e

^ A ^

p

h

Rapid β scission of the 1,3-biradical results in the formation of the C=0 and P=0 π bonds and yields the allylphosphonate, a product of the order 40 kcal/mol more Scheme IV Me I

254 nm quartz, CH and CH =CH-CH » with normal lifetimes, which would give product with deuterium scrambled between positions 1 and 3 of the allyl group. 2

2

2

Possible Radical Chain Mechanism. Potentially, the regiochemistry observed in Scheme V could result from afree-radicalchain mechanism, Scheme VI. However, a crossover experiment utilizing phosphites 1 and 2 failed to give so much as one percent of cross products (14). (MeO) P-0-CH -CH=CH 1 2

2

2

(MeO) P-0-CH -C(CH )=CH 2 2

2

3


2

140


Further evidence against kinetically freeradicalpairs is also provided by this finding. Scheme V H

(MeO) P^ J Q

2


0.2

hv 95%

D

2P(0). + CH =CH-CH OP(OMe) 2

2

2

Ο II

(MeO^P—CH —CH—CH -OP(OMe)2 2

2

Ο II

(MeO)2P-CH -CH—CH -j-OP(OMe)2 — (MeO) P-CH —CH=CH 2

2

2

2

2

+ (MeO) P(0> 2

0.6 M p-xylene, and also gave a 70% yield of phosphonate in the presence of pxylene versus a 25% yield in its absence. This suggested (14) that two mechanistically different processes are operative under the two conditions. Indeed pxylene is a favorite triplet sensitizer of photochemists who study alkenes possessing high triplet energies (15). When the deuterium-labeled allyl phosphite of Scheme V was irradiated directly in cyclohexane with 254 nm light, the deuterium in the phosphite was nearly totally scrambled indicating that the singlet state rearrangement involves a combination of what are formally 1,2- and 2,3-sigmatropic shifts. The phosphite did


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not undergo deuterium scramble under conditions of the photorearrangement nor did the product phosphonate (S.G. Lee, unpublished results, this laboratory). Effects of Sensitizer and Suggested Mechanism. The 2-phenylallyl functionality of the phosphite of Scheme VII typically has a triplet energy of about 62 kcal/mol Scheme V u

(MeOfePv^/*

254 nm cyclohexane

i


0.2 M

(MeO^ Ο

\ π

Φ direct =0.71

Ph * γ

ρ

(MeO^P^^A

η

350 nm, Pyrex 0.05 M Ph CO C6H

(MeO^P

2

l

6

Φ sens = 0.82

0.2 M

(16, 17) and is efficiently populated by benzophenone sensitization. Phosphite deuterium labeled at the CH 0 position of the allyl moiety gave the labeling results of Scheme VII and the quantum yields recorded. These results, previously published (14), appear to confirm the suggestions of the above work with benzene and p-xylene as photosensitizers. A possible mechanism for the triplet-sensitized photorearrangements is given in Scheme VIII. In the benzophenone-sensitized 2

Scheme VIII H A

(CHîO^^f

+

ISENS.*rTi

"

(CHjO^R^J

o-

σο

(CHjO)^

o f -

~ -

(CH 0)2P 3

X

J

o-y PHOSPHORANYL 1,3-BIRADICAL

T

( l)

reaction, the 1,2-scheme VII biradical-like triplet attacks phosphorus to form a phosphoranyl 1,3-biradical that after spin inversion gives product phosphonate by



142

scission of the C-O bond. A sensitizer with a very high triplet energy, such as benzene or p-xylene, is required for the unsubstituted or 2-methylallyl phosphites (Scheme V), whereas benzophenone is ideal for the dimethyl 2-phenylallyl case of Scheme VIII. Phosphites undergo reaction with ketones (sometimes sluggishly) when an efficient energy transfer is not available (78, 79). Direct irradiation of dimethyl 2-phenylallyl phosphite at 254 nm led to product with scrambled label (Scheme VII), a result analogous to that observed with dimethyl allyl phosphite (S.G. Lee, unpublished results, this laboratory).


Related Photoreactions The above examples apppear to be the first cases of intramolecular reactions of electronically excited alkenes with three-coordinate phosphorus. The intermolecular reaction of triplet 1,1-diphenylethene with a diphosphine is represented in Scheme DC (20). In this process the primary carbon of the radical-like triplet is responsible Scheme IX

Ph C-CH 2

Ph C-CH —PPh 2

2

2

+ PPh

(Ti)

2

2

Ph C=CH—PPh + Ph PH 2

Ph C-0 2

P(OEt)2

—

("PiOEt),

2

2

Ph C-OP(OEth 2

+

Ο j>II P(OEth

(ESR)

#

1

k = 8.0 χ KftvrV at 300°K(27) for a substitution reaction at phosphorus which is followed by a disproportionation. A phosphoranyl monoradical may be a transient intermediate. Several reactions of excited states of ketones (see Scheme IX (27)), quinones and thioketones with threecoordinate phosphorus are now known (22 26) in addition to the above-mentioned photorearrangements of β-ketophosphites (70). Attempted Extensions to Other Unsaturated Phosphites Attempts to extend the photorearrangements depicted in Schemes IV, V and VII to the phosphite featuring methyl substitution, 3, led to a very sluggish reaction yielding both regioisomers in overall yields less than 10% (W.Z. Ye, unpublished results,


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this laboratory). The result is reminiscent of the failure of isopropyl radicals to give

Ο 3 net reaction with even a benzyl phosphite via the potential process shown below (E.R. Hansen, P.E. Rogers, unpublished results, this laboratory). By contrast primary ethyl radicals react to give EtP(0)(OEt) , because a very rapid β scission step traps the intermediate phosphoranyl radical (E.R. Hansen, P.E. Rogers, unpublished results, this laboratory, cited in (27)). Downloaded by EMORY UNIV on April 18, 2016 | http://pubs.acs.org Publication Date: April 7, 1992 | doi: 10.1021/bk-1992-0486.ch011

2

— - (MeO) PCHMe Ο + PhCH * 2

2

2

(no net reaction) Scheme X shows the result of phenyl rather than methyl substitution. Sensitization led to no net reaction. Strikingly, direct irradiation yielded both Scheme X

Ph CO sens. 2

(MeO^P Ο

cis-trans isomerization only

Ph

Ph direct irradiation

gives both isomers Ph

Ο



144


regioisomers in a ratio of approximately 70/30 in favor of the phosphonate with primary carbon bonded to phosphorus (S.G. Lee unpublished results, this laboratory). The mechanism of this reaction, i.e. whether it involves a radical pair or competitive concerted processes, is unknown. Disappointingly, attempts at photorearrangement of phosphites containing homologated alkene chains did not reveal any new process analogous to that depicted above (S.G. Lee, unpublished results, this laboratory). This was true even when the chain was phenyl-substituted in attempt to favor the β scission reaction to give a 1,3-carbon biradical which is benzylic at one position (Scheme XI). Instead of the cyclopropyl-containing phosphonate, the product of a 1,2-shift resulted cleanly. This is an example of the photo-Arbuzov rearrangement of benzyl phosphites discovered in this laboratory (28, 29). The unsaturation in the chain is not needed for the reaction. Scheme XI

Cyclic Allyl Phosphites Reaction Scope. Extension of the allyl phosphite photorearrangment to five- sixand seven-membered ring compounds of the sort shown below with R = Η or Me gave some surprising results. Five- and six-membered ring compounds yielded no allylphosphonates at all and were consumed only extremely slowly in either benzene or cyclohexane. Substitution of a phenyl group at carbon 2 of the allyl chain rendered the six-membered ring phosphite susceptible to a sluggish rearrangement at 254 nm in benzene. The compound, however, unlike the acyclic compound, (MeO) POCH C(Ph)=CH , underwent extremely inefficient photosensitization by benzophenone. Increase of the ring size to seven resulted in a 2-phenylallyl, 2methylallyl and allyl phosphites that were photorearranged by direct photoirradiation at 254 nm, though still somewhat more slowly than the acyclic case. 2

2

2


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Moreover, benzophenone photosensitization with the seven-membered, 2-phenyl material succeeded, but relatively inefficiently. These are obviously only qualitative results and must be verified by careful quantum yield determinations. Nonetheless, the apparent order of reactivity in both direct and benzophenone-sensitized reactions is: acycliosevenring>sixring>fivering.(M. Tabet, W. Baik, Y.W. Wu, unpublished results, this laboratory). The regiochemistry of rearrangement of the six-membered ring 2-phenyl molecule under direct irradiation at 254 nm was not selective, giving essentially complete scrambling of deuterium. This mirrors the findings with the acyclic 2phenylallyl molecule. However, the seven-membered ring phosphite slowly gave product phosphonate regiospecifically under benzophenone-sensitized conditions. The latter result is consistent with the operation of an electrocyclic process similar to that depicted in Scheme VII. The photorearrangement of the seven-membered ring 2-phenylallyl phosphite displayed a regiochemistry on direct irradiation in benzene or CH CN that was strongly wavelength dependent Thus, by use of lamps with intensity peaking at 350 nm in a Rayonet reactor, phosphonate arising from regiospecific rearrangement resulted. Observed was what is formally a 2,3-sigmatropic rearrangement via a fivemembered ring intermediate or transition state. At 254 nm in benzene the label in the phosphonate was nearly completely scrambled. Controls evidenced the lack of scramble of label in starting phosphite or product phosphonate. (M. Tabet, unpublished results, this laboratory). 3

Mechanistic Implications. If the transfer of triplet energy from benzophenone to the various 2-phenylallyl phosphites is highly efficient in all cases, then the order of reactivity of the triplet allyl functionality decreases when two oxygens of the phosphite are part of a ring and as die ring becomes smaller. A possible understanding of the above may be gained from knowledge concerning the permutations of phosphoranyl monoradicals. Exchange of substituents between apical and equatorial positions in near-trigonal-bipyramidal phosphoranyl radicals, such as those shown below, involving the ligands that are not part of the ring (I * Π), occurs

II

I

k

6

ring

8

1

= 10 - 10 s- at273°K

ffl


146


rapidly by a mode 4 process (M4-exo), as measured by ESR (X,-Y = halo, alkoxy, amino, etc.). Rate constants are in the range 10 -10 s* at about 200 °K (7-4). The same sort or exchange for oxygens attached to phosphorus as part of a fivemembered ring (M4-ring, I - Π) is slower with ÎOMO s" at 273 °K (1-4). 7

9

1

8

1

By contrast for the spiro radical, shown below (TV), ligand exchange is relatively slow. No exchange is observed even at 393 °K from which it has been estimated that k„ is less than 10 -10 even at 393 °K (1-4). 6


' IV

o

7

Ο P

A », *

ΙΠ

V

'

O - P -

lower energy

A

\

IV Wavelength Effects Little has been said to now about the change in regiochemistry of the photorearrangements of the acyclic dimethyl 2-phenylallyl phosphite and its sevenmembered ring counterpart with variation in wavelength on direct irradiation. In the former case the wavelength was varied by using a medium pressure Hg lamp and cutoff filters. The cyclic phosphite was irradiated by lamps with maximum intensity


11. BENTRUDE


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at 350 nm and those with only the Hg resonance line at 254 nm. It is well known that the are several singlets accessible for alkenes (75), and two at accessible wavelengths for styrènes (30). The higher levels of course are populated by absorption of shorter wave lengths. Indeed, variations in the photochemistry of olefins as a function of wavelength are well established (37,52). Quite possibly a lower energy singlet, populated at longer wavelengths, undergoes exclusively what is formally a 2,3-sigmatropic shift. (No conclusion as to whether there is a discrete intermediate in the process is intended.) Higher energy singlets perhaps then give rise to the formal equivalent of a 1,3-sigmatropic shift or a combination of 1,3- and 2,3processes.


Summary With the provision that a number of the above reaction systems are subject to more careful study (for example the determination of quantum yields and the efficiency of triplet sensitization), the following conclusions arise, some of which are tentative. For what appear to be rearrangements via triplet excited states: 1) the regiospecificity is essentially complete resulting in what is formally a 2,3-sigmatropic shift; 2) since such a process must be stepwise, the postulation of the intermediacy of a phosphoranyl 1,3-biradical is reasonable; 3) substitution of the terminal alkene position with Ph or Me leads to very sluggish (Me) phosphonate formation or none at all (Ph); 4) reaction efficiency is reduced with phosphorus in a ring in the order. 7-ring>6-ring>5-ring. The presumably singlet state, direct irradiation processes are regiospecific at longer wavelengths (2-Ph cases) but give increased amounts of 1,2sigmatropic shift product at shorter wavelengths (254 nm, unsubstituted and 2-Ph cases). The mechanistic details of the singlet processes are yet to be defined. Acknowledgments. I would like to express my thanks to the following members of my research group who have carried out the studies described: Drs. Y. Charbonnel, K. Akutagawa, S.G. Lee, W. Baik, and Y.W. Wu; Professor W.Z. Ye; and Mr. M . Tabet. Generous support has been provided by the National Science Foundation and the National Cancer Institute of the Public Health Service, Grant CA11045. Literature Cited 1. 2. 3. 4. 5. 6. 7

Bentrude, W.G. In The Chemistry of Organophosphorus Compounds; Hartley, F.R., Ed.; John Wiley & Sons: New York, 1990; pp. 531-566. Bentrude, W.G. In Reactive Intermediates; Abramovitch, R.A., Ed.; Plenum Press: New York and London; 1983; Vol. 3; pp. 199-298. Bentrude, W.G. Acc. Chem. Res., 1982, 15, 117. Roberts, B.P. In Advances in Free Radical Chemistry; Williams, G.H., Ed.; Heyden: London; 1979; Vol. 6; pp. 225-284. Soldovnikov, S.P.; Bubnov; N.N.; Prokof'ef; A.I. Russ. Chem. Rev. 1980, 49, 1. Schipper, P.; Janzen, E.H.J.M.; Buck, H.M. Top. Phos. Chem. 1977, 9, 407. Bentrude. W.G. In Free Radicals; Kochi, J.K, Ed.; Wiley-Interscience: New York: 1973; Vol. 2; Ch. 22.


148



8. 9.

Walling,C.;Pearson, M.S. Top. Phosphorus Chem. 1966, 3, 1. Bentrude, W.G.; Kawashima, T.; Keys, B.A.; Garroussian, M.; Heide, W. Wedegaertner, D.A.J.Am. Chem. Soc. 1987,109,1227. 10. Griffin, C.E.; Bentrude, W.G.; Johnson, G.M. Tetrahedron Lett. 1969, 969. 11. Hornback, J.M.; Proehl, G.S.J.Am. Chem. Soc. 1979,101,7367. 12. Scully, F.; Morrison, H.J.Chem.Soc.,Chem. Commun. 1973, 529. 13. Unpublished results of P.J. Kropp, recorded in ref. 15. 14. Bentrude, W.G.; Lee, S.-G.; Akutagawa, Κ.; Ye, W.; Charbonnel, Y. J. Am. Chem. Soc. 1987,109,1577. 15. See examples recorded in the review of Kropp, P.J. Org. Photochem. 1979, 4, 1. 16. Crosby, P.M.;, Dyke, J.M.; Metcalfe, J.; Rest, A.J.; Salisbury, K.; Sodeau, J.R. J. Chem. Soc. Perkin Trans 2 1977, 182. 17. Lamola, A.A.; Hammond, G.S.J.Chem. Phys. 1965, 43, 2129. 18. Fox, M.A. J. Am. Chem. Soc. 1979,101,5339. 19. Chow, Y.L.; MarciniakJ.Org. Chem. 1983, 48, 2910. 20. Okazaki, R.; Hirabayashi, Y.; Tamura, K.; Inamoto, N.J.Chem.Soc.,Perkin Trans 1 1976, 1034. 21. Alberti, Α.; Griller, D.; Nazran, A.S.; Pedulli J. Org. Chem. 1986, 51, 3959. 22. For a review see Creber, K.A.M.; Chen, K.S.; Wan, J.K.S. Rev. Chem. Intermed. 1984, 5, 37. 23. For a review see Pedulli, G.F. Rev. Chem. Intermed. 1986, 7, 155. 24. Okazaki, R.; Tamura, Y.; Hirabayashi, Y. Inamoto, N.J.J.Chem.Soc.,Perkin Trans. 1 1976, 1924. 25. Alberti, Α.; Hudson, A. Pedulli, G.F.; McGimpsey, W.G.; Wan, J.K.S. Can. J. Chem. 1985, 63, 917. 26. McGimpsey, W.G.; Depew, M.C.; Wan, J.K.S. Phosphorus Sulfur 1984, 21, 135. 27. Bentrude, W.G.; Fu, J.J.L.; Rogers, P.E. J. Am. Chem. Soc. 1973, 95, 3625 28. Omelanzuk, J.; Sopchik, A.E.; Lee, S.G.; Akutagawa, Κ.; Cairns, S.M.; Bentrude, W.G.J.Am. Chem. Soc. 1988,110,6908. 29. Cairns, S.M.; Bentrude, W.G. Tetrahedron Lett. 1989, 30, 1025. 30. Crosby, P.M.; Dyke, J.M.; Metcalfe, J.; Res, A.J.; Salisbury, K.; Sodeau, J.R. J. Chem. Soc. Perkin Trans 2 WIT, 182. 31. Inoue, Y.; Dainal, Y.; Hagiwara, S.; Nakamura, H.; Hakushi, T.J.Chem. Soc., Chem. Commun. 1985, 804. 32. Inoue, Y.; Mukai, T.; Hakushi, T. Chemistry Letters 1983, 1665. RECEIVED November 12, 1991


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