J. Org. Chem. 1992,57,701-708 mixture was stirred at -78 OC for 15 min. A solution of the arenesulfonyl fluoride (0.57 mmol, p-toluenesulfonyl fluoride unleas otherwise noted) in anhydrous THF (2 mL) was then added slowly. The mixture was allowed to warm to rt and stirred for the given period of time. Normal workup was followed. General procedure E was followed for the following reactions. Methyl p-Tolyl Sulfone (3a, Table I, Entry 35). Reaction time: 18 h. Sulfone 3a was obtained in 86% yield. n-Butyl p-Tolyl Sulfone (3b, Table I, Entry 36). Reaction time: 18 h. Sulfone 3b was obtained in 88% yield. --Butyl p-Tolyl Sulfone (3d,Table I, Entry 37). Reaction time: 36 h. Sulfone 3d was obtained in 34% yield. tert-Butyl p-Tolyl Sulfone (3e, Table I, Entry 38). Reaction time: 18 h. Sulfone 38 was obtained in 17% yield. Phenyl p-Tolyl Sulfone (3f, Table I, Entry 39). Reaction time: 24 h. Sulfone 3f was obtained in 94% yield. Preparation of 2-Pentyl p-Tolyl Sulfone (5) via Treatment of p-Toluenesulfonyl Fluoride (la) with n-BuLi (2 equiv) Followed by Methyl Iodide. n-Butyllithium (0.60 mL, 1.21 mmol) was added dropwise over 5 min to a rapidly stirred solution of p-toluenesulfonyl fluoride la (0.10 g, 0.57 mmol) in anhydrous THF (10 mL) at -78 "C. The solution was stirred at -78 OC for 20 min and then alkylated with a solution of Me1 (0.20 mL, 2.87 mmol) and HMPA (0.20 mL, 1.15 mmol) in anhydrous THF and stirred for 30 min. The normal workup was followed giving sulfone 5 (0.109 g, 84%)as a pale yellow oil: I R (CHCl,, lit?5) 1289,1136 cm-'. Preparation of 2-(2-Methylpentyl) p-Sulfone (6) via Treatment of p-Toluenesulfonyl Fluoride (la) with n-BuLi (3 equiv) Followed by Methyl Iodide. n-Butyllithium (0.80 mL, 1.72 mmol) was added dropwise over 5 min to a rapidly stirred solution of p-toluenesulfonyl fluoride la (0.10 g, 0.57 mmol) in anhydrous THF (10 mL) at -78 OC. The solution was stirred at -78 "C for 20 min and then alkylated with a solution of Me1 (0.20 mL, 2.87 mmol) and HMPA (0.20 mL, 1.15 "01) in anhydrous THF and stirred for 30 min. The normal workup was followed giving sulfone 6 (0.115 g, 89%) as a pale yellow oil: 'H NMR (CDC13,200 MHz) 6 7.81 (d, 2 H, J = 8.2 Hz), 7.41 (d, 2 H, J = (25)Colter, A. K.; Miller, Jr., R. E. J. Org. Chem. 1971,36,1898-1903.
701
8.2 Hz), 2.51 (s,3 H), 1.70-1.68 (m, 2 H), 1.37-1.02 (m, 2 H),1.34 (8, 6 H), 0.98 (t, 3 H, J = 7.3 Hz). [(p-Tolylsulfonyl)methylene]cyclohexane (7) via Treatment of p -Toluenesulfonyl Fluoride (la) and (Trimethylsily1)methyllithium Followed by Cyclohexanone. (Trimethylsily1)methyllithium (1.6 mL, 1.14 mmol) was added dropwise over 5 min to a rapidly stirred solution of p-toluenesulfonyl fluoride (la) (0.1 g, 0.57 mmol) in anhydrous THF (10 mL) at -78 "C and stirred for 2 h. Distilled cyclohexanone (0.06 mL, 0.63 mmol) was added dropwise over 5 min at -78 OC, and the reaction was allowed to warm to rt over 2 h. The normal workup was followed giving sulfone 7 (0.0844 g, 54%) as an oil: 'H NMR (CDCls, 200 MHz) 6 7.74 (d, 2 H, J = 8.0 Hz), 7.28 (d, 2 H, J = 8.0 Hz), 6.11 (8, 1 H), 2.71 (br s , 2 H), 2.39 (s,3 H), 2.10 (br s, 2 H), 1.53 (br 8, 6 H). Registry No. 2a, 15310-28-8;2b, 94265-66-4;2k, 72834-71-0; 3a, 3185-99-7;3b, 7569-36-0; 3c, 136828-00-7; 3d, 91968-80-8; 3e, 5324-90-3; 3f, 640-57-3;3g,127-63-9; 3h, 42756-18-3; 34 1389421-8; 3j, 67963-06-8; 3k, 91358-89-3; 31, 3112-87-6; 3m, 5535-52-4;5, 29182-783;6,13682801-8; 7,136828-02-9;1 (Ar = p-Tol),45516-3; 1 (Ar = Ph), 368-43-4; MeLi, 917-54-4; n-BuLi, 109-72-8; TMSCHzLi, 1822-00-0; s-BuLi, 598-30-1; t-BuLi, 59419-4; PhLi, 591-51-5; Ph,CLi, 733-90-4; T M S C e L i , 54655-07-1; MeMgC1, 676-58-4; n-BuMgC1,693-049; PhMgBr, 100-58-3; H C s M g B r , 4301-14-8; cyclo-C8HllMgC1, 931-51-1; i-BuMgC1, 5674-02-2; aUylMgC1,2622-05-1;vinyUlgBr, 1826-67-1;MezCuLi, 15681-48-8; n-BuzCuLi, W 1 6 - 4 ; (TMSCHJ,CuLi, 40988-97-4;s-BuzCuLi, 23402-73-5; t-Bu,CuLi, 23402-75-7;PhzCuLi, 23402-69-9;n-BuCuSPhLi, 53128-68-0; Me2CuMgCl,67234-12-2;n-BuzCuMgC1, 60101-92-0; PhzCuMgBr, 58938-91-3; (cyclo-C6H11)&uMgC1, 62280-27-7;i-BuzCuMgCl, 136828-04-1; (allyl)zCuMgC1,9155088-8; n-BuPhSCuMgCl, 90384-66-0;MeCu, 1184-53-8;n-BuCu, 34948-25-9; S-BuCU, 89828-30-8; t-BuCu, 56583-96-1; PhCu, 3220-49-3; allylcu, 3797418-8; n-BuCuP(n-Bu)3, 26679-41-4; copper(1) iodide, 7681-65-4; cyclohexanone, 108-94-1. Supplementary Material Available: Elemental analysis results and spectral data on compounds 2a,b, 2k, 3a-g, 3i,j, 31, and 5-7 (3 pages). Ordering information is given on any current masthead page.
Branched Triangulanes: General Strategy of Synthesis Nikolai S. Zefirov,*It Sergei I. Kozhushkov,+Bogdan I. Ugrak? Kirill A. Lukin? Olga V. Kokoreva,t Dmitry S. Yufit,; Yury T. Struchkov? Stephan Zoellner," Roland Boese,s and Armin d e Meijere*i" Department of Chemistry, Moscow State University, 119899, Moscow, USSR, Nesmeyanov Institute of Organoelement Compounds, 117813, Moscow, USSR, Institut fiir Anorganische Chemie der UniversitBt-GH Essen, 0-4300 Essen, Germany, and Institut fur Organische Chemie, Georg-August-Universitat Gdttingen, 0-3400 Gdttingen, Germany Received June 20,1991
A general synthetic strategy for the construction of branched triangulanes (BTs) (spirocondensed polycyclopropanes) has been elaborated. The synthetic utility of the method is illustrated by the synthesis of some members of the [5]-and [6]BT families, especially 13a,b and 14. An independent synthesis of the perspirocyclopropanated spiropentane 14 is also presented.
The so-called triangulanes, hydrocarbons consisting exclusively of spiro-attached three-membered rings,l have interesting stereochemical implications, as elaborated for their simplest subclass, that of unbranched triangulanes (UTs) l.1-3 UTs can be prepared by the addition of chloromethylcarbene to
methylenecyc~opropanes,~,4-6
subsequent dehydrochlorination with potassium tert-butoxide in D M S O , ~ Yand ~ @final ~ cyclopropanation of t h e (1)Ffirov, N.S.;Kozhushkov, S. I.; Kuznetsova, T. S.; Kokoreva, 0. SOC. 1990,1123 €3.1.;Tratch, s. s. J. Am. 7702. 12) Zefirov. N.S.: K. A.: S. I.: , Lukin. - -..., -- . ., Kozhushkov. - -. -.. __._ - ,- ,Kuznetsova. -. __ - _,T. - R.: Domarev, A. M.; Sosonkin, I. M. Zh. Org. Khim. 1989,25,312. (3) For earlier syntheses of simple UTs, Bee: (a) Fitjer, L.; Conk, J.-M. Angew. Chem. 1973,&5,349,832; Angew. Chem., Int. Ed. Engl. 1973,12, 330,761. (b) Dolbier, W.R.; Akiba, K.; Riemann, J. M.; Harmon, C. A.; Bertrand, M.; Bezaguet, A.; Santelli,M. J.Am. Chem. SOC.1971,93,3933. (4) Arora, S.; Binger, P. Synthesis 1974,801. (5) Erden, I. Synth. Commun. 1986,16, 117.
v.;Lukm K.A.; uG& \-,
*Authors to whom correspondence should be addressed at Moacow State University or Georg-August-UniversitatGcttingen. 'Moscow State University. ._. Nesmeyanow_ _Institute. _8 Universitiit-GH Essen. 11 Georg-August-UniversitiitGBttingen.
*
0022-3263/92/1957-0701$03.00/0
0 1992 American Chemical Society
702
Zefirov et al.
J. Org. Chem., Vol. 57, No. 2, 1992
10 (I
11
12
(i) CHSCHC12/BuLi, (ii) t-BuOK/DMSO, (iii) CH2N2/Pd(OAc)p
Scheme I1 MeO(CH&CHCI2
la
Dc
/
nauu
\
MeO-
Pr
t
17a
16
1 19
t-BuOUJDMSO
20a
resulting methylenetriangulane with diazomethane in the presence of palladium(I1) acetate209J0(eq 1).
(1 1
(i) CH8CHCI2/BuLi, (ii) t-BuOKIDMSO, (iii) CH2N2/Pd(OAc)2 (6) Baldwin, J. E.; Parker, D. W. J . Org. Chem. 1987,52, 1475. (7)Hill, E.A.; Park, Y.-W. J . Organomet. Chem. 1988,356,1.
This sequence may also be applied to the synthesis of brunched triungulunes (BTs) 2, provided that alkenes of type 3 are available. Starting from bicyclopropylidene5,11 the simplest BT-[3]rotane 412-was prepared in this manner.2s5 More recently, this approach has been applied to the synthesis of triangulane 9, a member of the [5]BT family, and hydrocarbon 10, a member of the [6]BT family,
1
2
3
5 4 starting from methylene[4]UT 62,s (Scheme I). The structures of triangulanes 9 and 10 and methylenetriangulanes 8 and 11 were confirmed by their spectral characteristics as outlined in the Experimental Section. In this paper a general strategy is proposed for the preparation of BTs based upon the addition of substituted chloroethylcarbenes to methylenecyclopropanes as de(8)Pikulin, s.;Berson, J. A. J. Am. Chem. SOC.1988,110, 8500. (9) efirov, N.S.; Kozhushkov, S. 1.; Kuznetaova, T. S.; Lukin, K. A.; Kazimirchik, I. V. Zh. Org. Khim. 1988, 24, 673. (10)Chenier, P. J.: Southard, D. A. J. Ora. Chem. 1990.55.1669 and . . references therein. (11)(a) Le Perchec, P.; Conia, J.-M. Tetrahedron Lett. 1970,1587.(b) Fitjer, L.;Conia, J.-M. Angew. Chem. 1973,85,347;Angew. Chem., Int. Ed. Engl. 1973,12,332. (c) Schmidt, A. H.; Schirmer, U.; Conia, J.-M. Chem. Ber. 1976,109.2588. (d) Weber. W.:de Meiiere. A. Svnth. Commun. 1986,16,837. (12)For the first synthesis and some physical properties of [3]rotane, see: (a) Reference 3. (b) Gleiter, R.;Haider, R.; Conia, J.-M.; Bamier, J.-P.; de Meijere, A.; Weber, W. J. Chem. Soc., Chem. Commun. 1979, 130. (c) Pascard, C.; Prang6, T.; de Meijere, A.; Weber, W., Bamier, J.-P.; Conia, J.-M. J. Chem. SOC.,Chem. Commun. 1979,425.
J. Org. Chem., Vol. 57, No. 2, 1992 703
Branched Triangulanes picted in eq 2. The synthetic potential of this approach CI
is demonstrated by the preparation of some members of the [5]- and [6]BT families, namely, hydrocarbons 13a,b and 14.
n
U
Figure 1. General view of the molecule 14.
v
Table I. Bond Lengths (A) . . in Structure 14 C(l)-C(2) 1.481 (2) C(l)-C(3) 1.480 (2) C(2)-C(3) 1.477 (3)
13a
13b
14
Results and Discussion l,l-Dichloro-3-R-oxypropanes 15a,b (R = Me, tetrahydropyran-2-yl) have been prepared from known precursors by standard methods (see Experimental Section) and examined as potential carbenoid precursors for the [1 21 cycloadditionto methylenecyclopropanes. In fact the carbenoid generated by the action of sodium bis(trimethylsilyl)amide4 on 15a adds to the double bond of methylenecyclopropane (16) to give the desired spiropentane derivative 18a in good yield, whereas n-BuLi reacts with the carbenoid13 to give 17a (Scheme 11). Dehydrochlorination of chloride 18a with potassium tertbutoxide in DMSO at 60 "C was accompanied by allylic rearrangementI4 to afford enol ether 19; but a t ambient temperature within 15 h a Z / E mixture of olefin 20a is obtained. Schemes I11 and IV illustrate the application of this strategy to the synthesis of the novel branched triangulanes 13a,b and 14. Note that the method is successful only when R in the carbenoid precursor and ita products 18-25 is a THP (tetrahydropyranyl)group. When R is a methyl group, efforts to remove the protecting group in compound 25a with FeCl Ac20,15P0Cl3/DMFl6 (20 O C , 24 h), and Me3SiC1/Na113/ (20 "C) were unsuccessful; with pure Me3SiIU (-30 OC) a 5.8% total yield of olefins 28a,b was isolated by column chromatography on silica gel after dehydroiodination of the resulting mixture of iodides with t-BuOKIDMSO. Chlorination of alcohol 26 (CC14/PPh3, 20 "C, 96 h19) was incomplete (-lo%), but bromination with subsequent dehydrobromination gave the desired
+
~
~
~~
~~~~~
(13) Kirmse, W.; v. Biilow, B . 4 . Chem. Ber. 1963, 96,3316, 3323. (14) Prosser, T. J. J. Am. Chem. SOC.1961, 83, 1701. (15) Ganem, B.; Small, V. R. J. Org. Chem. 1974, 39, 3728. (16) Lonchakova, T. I.; Vuzykin, B. I.; Tsivunin, V. S. Zh.Org. Khim. 1974. 10., 2459. ~ ~ (17) Olah,G.A.; Narang, S. C.; Gupta, B. G.B.; Malhotra, R. J. Org. Chem. 1979,44, 1247. (18) Jung, M. E.; Lyster, M. A. J . Org. Chem. 1977, 42, 3761. (19) Snyder, E. I. J . Org. Chem. 1972, 37, 1466. ~
~I
C(2)-C(6) 1.486 (3) C(2)-C(7) 1.482 (3) C(3)-C(4) 1.480 (3)
C(3)-C(5) 1.484 (3) C(4)-C(5) 1.532 (3) C ( 6 ) 4 ( 7 ) 1.532 (3)
Table 11. Bond Lengths (A) in Structure 32 (Mean Values for Four Indewndent Molecules) O(1)-C(l2) C(l)-C(2) C(l)-C(3) C(l)-C(8) C(l)-C(9) C(2)-C(3)
1.431 (4) 1.482 (5) 1.478 (5) 1.515 (5) 1.465 (5) 1.476 (5)
C(2)-C(6) C(2)-C(7) C(3)-C(4) C(3)-C(5) C(4)-C(5) C(6)-C(7)
1.485 (6) 1.481 (6) 1.485 (6) 1.483 (6) 1.542 (6) 1.541 (6)
C(8)-C(9) C(B)-C(l2) C(9)-C(lO) C(9)-C(ll) C(lO)-C(ll)
1.506 (6) 1.512 (6) 1.487 (6) 1.491 (6) 1.540 (61
olefins 28a,b (2.21 mixture of anti and syn isomers), which partially decomposed upon distillation. Cyclopropanation of this substance afforded a mixture of hydrocarbons 13a,b in a ratio of 1.4:l. The stereoisomers 13a,b were identified on the basis of their 13CNMR spectra, taking into consideration the total symmetry of the molecules. Triangulane 13a has a C2axis, and the isomer 13b possesses a symmetry plane. Thus, carbon atoms C" and C12 are to be equivalent in the 13C NMR spectrum of the anti isomer 13a and nonequivalent in that of the syn isomer 13b. Based on the fact that compound 13a was produced from olefin 28a (13b from 28b) and that the major isomer in the mixture was 13a, spectral assignments for the mixture of anti- and syn-methylenetriangulanes 28a,b were made. The consideration of the molecular symmetry (C,axis in 28a and symmetry plane in 28b) leads to the same spectroscopic results in this case. This same methodology was used for the synthesis of the branched triangulane 14 starting from bicyclopropylidene 512 (Scheme IV). All compounds depicted in Scheme IV were obtained in satisfactory yields. As in the previous sequence the methyl group in ether 33a could not be removed without destruction of the skeleton, but the acetal 33b could smoothly be converted to alcohol 34. The highly symmetrical (symmetry point group DZd) triangulane 14 shows only three signals in ita 13C NMR spectrum and a few signals in the 'H NMR spectrum. The [6]BT 14, a fully spirocyclopropanated spiropentane, was independently synthesized by reaction of in situ generated diazocyclopropaneZ0with the known bi-
~
(20) Cf. (a) Fitjer, L.; Conia, J.-M. Angew. Chem. 1973,85,349;Angew. Chem.,Int. Ed. Engl. 1973,12,334. (b) Kirmse, W.; SchOtte, H. Chem. Ber. 1968,101, 1674.
Zefirov et al.
704 J. Org. Chem., Vol. 57, No. 2, 1992 Scheme I I P b
21 a,b
20 a,b
18a,b
I
ii
ROH2C-
ROH2C'
22 a,b
24 a,b
23 a,b
*- -* I
iii
vi
iV
CH2OR
25 a,b
13a,b
CH20H
6H2Br
26
27
iii
. *
28a
28b
a (a) R = Me; (b) R = -CH(CH2)40. (i) CH&HCI,/BuLi, (ii) t-BuOKIDMSO, (iii) CH2N2/Pd(OAc)2,(iv) HCl, (v) RO(CH2)2CHC12 (1Sa,b)/NaN(SiMe3)2,(vi) Ph3PBr2/Py.
cyclopropylidene derivative 3721(Scheme V). Except for unreacted starting material (51%), 14 was isolated as the sole product (23% yield). The same approach has been used t o prepare t h e [8]BT heptaspiro[2.0.0.2.0.2.0.0.0.2.0.2.O.O]heptadecane(41) along with 11cyclopropylidenetetraspiro[2.0.0.2.0.2.O.l]undecane (40) and bi(trispiro[2.0.2.l]heptylidene) (39).22 The molecular geometries of compounds 14 and 32 were confirmed by X-ray crystal structure analyses (Figures 1 and 2). The most interesting features of these molecules are the lengthening of distal bonds opposite the four external spiro carbon atoms of the central spiropentane unit and the shortening of bonds involving these atoms (Tables I and 11). This difference in bond distances is the same as observed for ~ p i r o p e n t a n eand ~ ~ [3]r0tane~~ and in agreement with ab initio calculations at the STO-3G level.% Fitjer, L. Chem. Ber. 1982, 115, 1035,1047. (22)Zoellner, S.; Boese, R.; Gleiter, R.; de Meijere, A. Angew. Chem.
(21)
In Dress. (23)Boese, R.; Blaeser, D.; Gomann, K.; Brinker, U. H. J. Am. Chem. SOC.1989, 111, 1501. (24) Boese, R.; Miebach, T.; de Meijere, A. J. Am. Chem. SOC.1991, 113, 1743. ~~~
U
Figure 2. General view of one independent molecule 34.
The lengthening of the distal bonds is apparently due to increased angular strain a t the spiro carbons and the
Branched Triangulanes
J. Org. Chem., Vol. 57, No. 2, 1992 705
Scheme IV"sb
Scheme V
5
[D=N~ ]
1.
mpentane
14
37 29 a,b
30 a,b
31 a,b
38 32
33 a,b
39
34 a,b
P
+34+A* D
40
41
infiiite chains with hydrogen bonds along the b direction (Figure 3). "(i) (a) R = Me; (b) R =
