J. Org. Chem., Vol. 40, No. 5, 1975 585
Mercuric Ion Catalyzed Rearrangements of Allenes Registry No.-1, 7688-03-1;3, 53684-33-6;5, 19372-00-0;6, 53684-34-7; 7, 22031-64-9;8, 53684-35-8;9, 14629-58-4;10, 5368414, 53684-38-1;16, 53684-39-2; CSI, 1189-7136-9;11, 53684-37-0; 5;trans-cinnamonitrile, 1885-38-7; /3-phenethyl alcohol, 60-12-8. References and Notes (1) (a) C. Eaborn and R. W. Bott, "Organometallic Compounds of the Group IV Elements," Vol. I, A. MacDiarmid, Ed., Marcel Dekker, New York, N.Y., 1968, pp 392-395; (b) K. E. Koenig and W. P. Weber, J. Amer. Chem. Soc., 95, 3416 (1973); (c) K. E. Koenlg and W. P. Weber, Tetrahedron Lett., 2533 (1973); (d) G. Stork and E. Calvin, J. Amer. Chem. Sac., 93, 2080, (1971); (e) G. Stork and M. E. Jung, ibid., 96, 3682 (1974); (f) B. Grobel and D. Seebach, Angew. Chem., ht. Ed. Engl., 13, 83 (1974). (2) L. A. Paquette, G. R. Ailen, and M. J. Broadhurst, J. Amer. Chem. SOC., 93, 4503 (1971). (3) (a) T. J. Barton and R. J. Rogldo, Tetrahedron Left., 37, 3901 (1972); (b) J. R. Malpass and N. J. Tweddle, Chem. Commun., 1244 (1972); (c) T. W.Doyle and T. T. Conway, Tetrahedron Lett., 1889 (1969); (d) L. A. Paquette and G. R. Krow, J. Amer. Chem. Soc., 91, 6107 (1969); (e) E.
Dunkelblum, Tetrahedron Lett., 1551 (1972); (f) D. J. Pasto, A. E. Chen, G. Ciurdaru, and L. A. Paquette, J. Org. Chem., 36, 1015 (1973); (9) D. J. Pasto and A. F. Chen, TetrahedronLett., 713 (1973). (4) A. G. Brook, Accounts Chem. Res., 7, 77 (1974). (5) L. H.Sommer, eta/., J. Amer. Chem. SOC.,76, 1613 (1954). (6) T. J. Barton and R. J. Rogido, J. Chem. SOC., Chem. Commun., 878 (1972); Tetrahedron Lett., 3901 (1972). (7) T. J. Barton, R. C. Kippenhan. Jr., and A. J. Nelson, J. Amer. Chem. SOC.,96, 2272 (1974). (8) L. M. Jackman and S. Sternhell, "Application; of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2nd ed, Pergamon Press, London, 1969, p 198. (9) T. J. Barton and E. E. Gottsman, Syn. lnorg. Metal-Org. Chem., 3, 201 (1973). (IO) R. A. Benkeser and R. A. Hickner, J. Amer. Chem. SOC., 80, 5298 (1958). (11) R. C. Weast, Ed.; "Handbook of Chemistry and Physics," 50th ed, Chemlcal Rubber Publishing Co., Cleveland, Ohio, 1969, p C-243. (12) R. T. Conley, "Infrared Spectroscopy," 2nd ed, Allyn and Bacon, Boston, Mass., -1972, p 78. (13) W. Gerrard and K. D. Kliburn, J. Chem. Soc., 1536 (1956). (14) R. Graf, Justus Liebigs Ann. Chem., 661, 111 (1963).
Mercuric Ion Catalyzed Rearrangements of Ten-Membered-Ring Allenssl Richard W. Thies,* Pak-Kong Hong, Richard Buswell, and Janice L. Boop Department of Chemistry, Oregon State University, Corvallis, Oregon 97331 Received October 2,1974 In contrast to most oxymercurations, the reactions of cyclodeca-1,2,5,8-tetraene, 3, and cyclodeca-1,2,5-triene, 7, with mercuric sulfate and acetic acid give only rearranged products. The major products from 8 are cis,syn-decalin-2-yl acetate, 4, and tricycl0[4.4.0.0~~~]deca-5,8-diene, 6. Compound 7 gives only tricycl0[4.4.0.0~~~]dec-5-ene, 8. The ratio of products for 3 depends on solvent nucleophilicity.
Oxymercuration is often used to effect Markovnikov addition of solvent to double bonds without rearrangement.2-4 In the case of nonterminal allenes, mercuric ion generally adds to give a mercurinium ion that is attacked by solvent so that the mercury is ultimately attached to the center allene carbon (eq 1).5-7 The mercury group can be
' A RH'C-C-CHR
SOH
I
I
-+ RHC-C-CHR
4
6
(1)
reductively removed4 'or is often lost during reaction under acidic conditions by an addition-elimination mechanism.7 Allene oxymercuration represents an important part of a general technique for ring expansion and functionalization of medium-sized rings.8 The cases herein reported are the only known examples of rearrangement during oxymercuration of an allene. The most closely related system studied is cyclonona-1,2,6triene (1) that was reported9 to give only the normal adduct, 2.
OEt
1
Treatment of 3 with mercuric,sulfate in acetic 'acid followed by reduction with lithium aluminum hydride did not lead to the expected allylic alcohol but to two rearranged alcohols, 4 and 5, and a rearranged hydrocarbon, 6. Similar
2
Results Cyclodeca-1,2,5,8-tetraene(3) was prepared from cyclonona-l,4,7-trienel0 by the method which involves addition of a dibromo carbenoid and subsequent conversion to the allene using methyllithium.8 Cyclodeca-172,5-triene (7) was prepared in a similar way from 1,4-cyclononadiene.l1
7
8
treatment of 7 gave only rearranged hydrocarbon 8. The carbon skeleton and stereochemistry of 4 were assigned by reduction to the known cis,syn-decaIin-2-01.~~ The locations of the double bonds were determined by spreading out the proton magnetic resonance spectra with Eu(fod)3 shift r e a g e n P and then performing decoupling experiments. The changes in chemical shift of the various protons with added shift reagent (Table I) are consistent with the assigned structure 4. Furthermore the H3 methylene protons were shown to be coupled to H2 and one vinyl proton (H4) which locates one double bond. The H1 proton was shown to be coupled with Hz and the Hlo methylene pair. Coupling was also demonstrated between the Hlo protons which locates the other double and a vinyl proton (HB) bond. (See Figure 1.) The structure of the minor alcohol product 5 was not fully elucidated, but hydrogenation followed by oxidation to the ketone gave cis-bicyclo[5.3.0]decan-2-one. Reduction of either hydrocarbon 6 or 8 gave cis- and trans-decalin. Other reactions of 6 such as ozonolysis, oxymercuration, epoxidation, and hydroboration gave intrac-
J. Org. Chena., Vol. 40, No. 5, 1975
586
Thies, Hong, Buswell, and Boop
Table I Chemical Shifts for cis,syn-Bieyclo[4.4.O]deca-4,8-dien-2-ol (cis,syn-Decalin-2-01) with Added Shift Reagenta
_ _ _ _ - - ~ Addd
Lu(f0d);
H2
HA
fi 3
H5
Hg
H8
H7
H10
E39 ~~
25
4 .O 5.2 7.9
70
13.1
100
16.5
0 5
a
2.5 3 .O 5.1, 4.8 9.2, 8 .O 11.6. 9.9
H1 ~
~~
(5.3-5.9) (5.4-5 -9) 6.3 6.0
(1.9-2.3) (2 .O-2.8) 3.4 2.6
(5.3-5.8) (5.4-5.9) 6.0 6.3
7.0 6.6
4.6 3.3
6.6 7.0
(6.8-7.7)
8.0 7.4
5.3 3.7
6.9 7.7
9.3, 9.4 8.6
(1.9-2.3) (2.03.8) (4.0-4.7)
The protons are numbered according to the carbon to which they are attached (see Figure 1). The chemical shift is given in 6.
9
3
9
9
8
4
8
8
Table XI Chemical Shifts for c i s , s y n , c i s - ~ i c ~ ~ l 0 [ .0.O2~*]dacan-anti-~-ol 4.4 with Increasing Amounts of Eu(fod)s Shift Reagenta
5
s 7
-___
OH 4
6
10
Figure 1. Numbering used for 4 and 6 and 10.
table material or complex product mixtures. The structure was assigned from its spectral data. The chemical shifts apd coupling patterns of the cyclopropyl protons are similar to those of bicyclo[3.l.0jhex-2-ene14 (see Experimental Section) which locates the cyclopropane ring and one double bond. The ultraviolet spectra, which shows only end absorption, rules out any conjugated isomers. This leaves two possible positions for the other double bond which are shown in structures 6 and 9. For compound 9, the chemical
9
cis, anti-6
a s , syn-6
shifts for the five protons which are nonvinyl and noncyclopropyl should appear as a group of four protons near 6 2.2 and one proton near 6 3.1. The observed chemical shifts for the compound that has been assigned as 6 are quite different, viz., one proton near 3.0, a rather sharp two-proton peak a t 2.8, a proton a t 2.5, and one hidden in the 6 1.4-2.0 group of cyclopropyl protons. The 6 2.8 pattern is presumably due to the doubly allylic protons (H7). The other three protons are near the rather strongly anisotropic cyclopropyl group. Using the reported shielding effects for that group,l5 the calculated chemical shifts for the allylic methylene and methine protons are 6 2.1, 2.3, and 2.4 for the cis,anti isomer and 1.6, 2.1, and 2.8 for the cis,syn isomer. The cis,syn isomer agrees reasonably well with the observed values (ea., 1.7, 2.5, and 3.0). In the calculated chemical shifts, it was assumed that in the absence of cyclopropane anisotropy, the methylene protons’ chemical shifts would be like cyclohexene (6 2.0) and that of the methine proton would be 6 0.3 down field of cyclopentene (2.3 0.3 = 6 2.6).16 Structure 8 was initially assigned by analogy with 6 and from the nmr spectrum which showed two high-field cyclopropyl protons and one vinyl proton. Confirmation of the structure and assignment of stereochemistry was obtained by conversion of 8 to 10 (see Figure 1) by hydroboration. Treatment of 10 with Eu(fod)3 shift reagent separated the protons at C1 to CGfrom the other protons in the spectrum.
+
H5
3.9 5.9 10 .0 11.6 12.6 1.5.9 17.0
‘36
b b 6.4 7.4 8.2 10.4 11.2
endo-
exa-
H4
HI
H2
H3
f33
b h 5.8 6.7 7.5 9.8 10.6
2.7 3.6 5.8 6.7 7.2 8.8 9.3
b h 3.5 4.0 4.4 5.4 5.7
0.6 1.1 2.2 2.8 3.1 4.0 4.3
0.5 0.8 1.8 2.1 2.3 2.8 3.1
a The protons in the six-membered ring are not shown. In the final entry they had separated into two four-proton groups at 6, 4.3 and 3.1. * Buried in a large multiplet.
Proton H5 appeared as a rather sharp singlet in agreement with previous studies of a similar system, syn- %deuteriumanti-2-bicyclo[3.1.0]hexano1,~* and with the model which showed dihedral angles close to 90O between H5 and its neighboring protons. No clear decoupling could be done with H5 but the Eu(fod)a shift studies showed t,hat one of the two closest protons to H5 was a cyclopropyl proton (H4) since decoupling established that it was coupled with the high-field cyclopropyl protons. Similar decoupling located Hz which in turn was shown to be coupled with the proton (HI) that has a shift of 2.75 in the unshifted spectrum. That proton appears a t unusually low field because of the rather strong anisotropy of the cyclopropane ring.15 Decoupling also established the link between H1 and the other “closest proton to €35.’’ The cis,syn,cis stereochemistry for 10 has been assigned from the small coupling constants to H5 and from the chemical shift changes when Eu(fod)3 was added (Table 11). Inspection of Drieding models indicates that only the assigned stereochemistry should have dihedral angles of about 90’ between H5 and both its neighhors. In addition, the distances between the europium (assumed to be 2.3 A on the C-0 axis17) and protons HI, Hz, H:+,Hq, and 136 could be fitted for that stereochemistry and not for the others. Using Hz to calculate a proportionality constant for the equation r 3 = kA6, the other distances were calculated. When the boatlike conformation of the five-membered ring (11)was used, all the calculated distances were within 0.1 of those measured from the model except enclo-H3 which differed by 0.3 A. All of the other possible stereochemistries had at least one proton that was off by a t least 1.0 The only other stereochemistry that could concievably have near-zero couplings to H5 is trans,anti,cis as shown in 12. The chemical shifts for 12 do not correlate well, espe-
a
a.
J. Org. Chem., Vol. 40, No. 5, 1975 587
Mercuric Ion Catalyzed Rearrangements of Allenes
Scheme I
Table I11 Productsa Formed from cis,cis-Gyclodeca-1,2,5,8-tetraene (3) Relative percentages Condition?
% yield
4
5
6
epi-4
13
HCO,H, HgS04 HCOZH HOAc, HgSOa HOAC, Hg(OAc), 60% aq acetone, HgS04
19
63
24 52 47
53
14 12 3
50
5
