Cumulated Trienephosphine Oxides. Bimolecular Trapping of an Alkylidenecyclopropylidene

Article abstract of DOI:10.1021/jo970771u

Dihalocarbene addition to allenic phosphine oxides occurs mainly at the allylic double bond. Treatment of dibromocarbene adducts with BuLi leads to cumulated trienephosphine oxides. In some cases, the intermediate alkylidenecyclopropylidene (or its precur

Full text of DOI:10.1021/jo970771u

J . Org. Chem. 1997, 62, 9039-9047
9039
Cu m u la ted Tr ien ep h osp h in e Oxid es. Bim olecu la r Tr a p p in g of a n
Alk ylid en ecyclop r op ylid en e†
Christiane Santelli-Rouvier,*,1 Lo¨ıc Toupet,2 and Maurice Santelli*,1
ESA au CNRS no. 6009, Centre de St-J e´roˆme, Av. Esc. Normandie-Niemen,
13397 Marseille Cedex 20, France, and Groupe Matie`re Condense´e et Mate´riaux, associe´ au
CNRS no. 804, Campus de Beaulieu, 35042 Rennes Cedex, France
Received April 30, 1997X
Dihalocarbene addition to allenic phosphine oxides occurs mainly at the allylic double bond.
Treatment of dibromocarbene adducts with BuLi leads to cumulated trienephosphine oxides. In
some cases, the intermediate alkylidenecyclopropylidene (or its precursor) is exceptionally stabilized,
and this carbene (or carbenoid) is trapped by the corresponding cumulated trienephosphine oxide
in a bimolecular process. The resultant spiropentane is formed in a regio- and stereoselective
manner.
In tr od u ction
relatively rapid equilibrium is probably established
between CCl3Li and dichlorocarbene at -70 °C, from
which the dichlorocarbene is removed by the alkene in a
rate-determining process.9
A large class of thermally unstable substances consists
of the R-haloorganolithium compounds.3 These carbenoid
compounds are exceptional because they react not only
with electrophiles as is usual for “anions” but also with
nucleophiles such as RLi4 and also eliminate LiX with
the formation of carbenes.
The electrophilic nature of carbenoids is perhaps their
most intriguing property. Seebach and co-workers have
shown that the carbenic character can be recognized by
the strong downfield shift in the 13C NMR signal of the
R-carbon atom5 (this is similar to that observed in
carbocations).
gem-Lithiohalogenocyclopropanes, which are stable at
temperatures around -100 °C, are important intermedi-
ates in organic synthesis. They can generally and
conveniently be obtained through halogen-lithium ex-
change in reactions of the dihalogenocyclopropanes with
alkyllithium.10 These metalated species are easily trapped
with electrophiles. At temperatures above -100 °C, the
lithiohalocyclopropanes are converted to singlet cyclo-
propylidenes by formal loss of lithium halide.
Occasionally the cyclopropylidene to allene isomeriza-
tion is disfavored for structural reasons; the reaction is
then forced to follow an alternative path.11,12 Despite a
number of investigations, the precise reaction mechanism
of the 1-halogeno-1-lithiocyclopropane opening to give
allene is not fully clear, and the formation of free
cyclopropylidene is questionable.13 The most recent
calculations indicate that the ring opening of cyclopro-
pylidene proceeds via disrotation until the Cs transition
state is reached at a C(1)-C(2)-C(3) angle of about 84.5°;
disrotation continues with maintenance of Cs symmetry
until a C(1)-C(2)-C(3) angle of about 100° is reached,
at which point the reaction surface bifurcates into enan-
tiomers via admixture of a conrotatory component,
ultimately leading to allene.14 The cyclopropylidene to
The reactivity and stereochemistry observed in the
reaction of these carbenoids has been interpreted by
Walborsky as being due to metal-assisted ionization
(MAI).6 Carbenoids react with alkyllithium to give
substitution products with inversion of configuration.
These results suggest that the halide is the leaving group
and not the lithium, thus leading to development of
positive charge on carbon and can be explained by the
reduction in the nucleophilicity of the carbanion with
substitution of R-chloro groups.
Reaction between CCl3Li and an olefin without inter-
mediate carbene formation was first indicated by the high
yields of 7,7-dichloronorcarane obtained by adding cy-
clohexene to CBrCCl3 and MeLi at -100 °C.7 The slow
decomposition of (trichloromethyl)lithium in THF at -72
°C is accelerated by cyclohexene and other olefins.8
A
(8) (a) Hoeg, D. F.; Lusk, D. I.; Crumbliss, A. L. J . Am. Chem. Soc.
1965, 87, 4147-4155. (b) Ko¨brich, G.; Flory, K.; Merkle, H. R.
Tetrahedron Lett. 1965, 973-978.
† Dedicated to the memory of Dr. I. D. R. Stevens, deceased
September 12, 1997.
X Abstract published in Advance ACS Abstracts, December 1, 1997.
(1) Faculte´ de St J e´roˆme. Fax: (33) 04 91 98 38 65. E-mail:
m.santelli@lso.u-3mrs.fr.
(9) Ko¨brich, G.; Bu¨ttner, H.; Wagner, E. Angew. Chem., Int. Ed.
Engl. 1970, 9, 169-170.
(10) For reviews on the use of gem-dihalocyclopropanes in organic
synthesis, see: (a) Backes, J .; Brinker, U. H. In Methoden der
Organischen Chemie (Houben-Weyl); Regitz, M., Ed.; Thieme Verlag:
Stuttgart, 1989; Vol. E19b. (b) Kostikov, R. R.; Molchanov, A. P.; Hopf,
H. Top. Curr. Chem. 1990, 155, 41-80. (c) Banwell, M. G.; Reum, M.
E. Adv. Strain Org. Chem. 1991, 1, 19-64.
(11) (a) Skattebøl, L. Tetrahedron Lett. 1970, 2361-2364. (b) Moore,
W. R.; Taylor, K. G.; Mu¨ller, P.; Hall, S. S.; Gaibel, Z. L. F. Tetrahedron
Lett. 1970, 2365-2368. (c) Moore, W. R.; Hill, J . B. Tetrahedron Lett.
1970, 4343-4346. (d) Moore, W. R.; Hill, J . B. Tetrahedron Lett. 1970,
4553-4556.
(2) Campus de Beaulieu. Address X-ray correspondence to this
author.
(3) (a) Ko¨brich, G. Angew. Chem., Int. Ed. Engl. 1967, 6, 41-52. (b)
Ko¨brich, G. Angew. Chem., Int. Ed. Engl. 1972, 11, 473-485.
(4) Topolski, M.; Duraisamy, M.; Rachon, J .; Gawronski, J .; Gawron-
ska, K.; Goedken, V.; Walborsky, H. M. J . Org. Chem. 1993, 58, 546-
555.
(5) (a) Seebach, D.; Siegel, H.; Mu¨llen, K.; Hiltbrunner, K. Angew.
Chem., Int. Ed. Engl. 1979, 18, 784-785. (b) Siegel, H.; Hiltbrunner,
K.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1979, 18, 785-786. (c)
Seebach, D.; Siegel, H.; Gabriel, J .; Ha¨ssig, R. Helv. Chim. Acta 1980,
63, 2046-2053. (d) Seebach, D.; Ha¨ssig, R.; Gabriel, J . Helv. Chim.
Acta 1983, 66, 308-337.
(12) (a) Moore, W. R.; Ward, H. R. J . Org. Chem. 1960, 25, 2073. (b)
Moore, W. R.; Ward, H. R.; Merritt, R. F. J . Am. Chem. Soc. 1961, 83,
2019-2020. (c) Marquis, E. T.; Gardner, P. D. Tetrahedron Lett. 1966,
2793-2798. (d) J ones, M., J r.; Petrillo, E. W., J r. Tetrahedron Lett.
1969, 3953-3956.
(6) Duraisamy, M.; Walborsky, H. M. J . Am. Chem. Soc. 1984, 106,
5035-5037.
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2089-2090.
(13) Warner, P.; Sutherland, R. J . Org. Chem. 1992, 57, 6294-6300
and references therein.
S0022-3263(97)00771-8 CCC: $14.00 © 1997 American Chemical Society

9040 J . Org. Chem., Vol. 62, No. 26, 1997
Santelli-Rouvier et al.
Sch em e 1
allene transition state is electron deficient and resembles
that for the cyclopropyl to allyl cation.
Cyclopropylidenes are transient metastable species and
the parent has not yet been isolated experimentally. The
energy barriers calculated15 for its conversion to allene
lie between 18 and 40 kcal mol-1 and are somewhat at
variance with the experimental observations. Thus
cyclopropylidene, generated by photolysis of matrix-
isolated cyclopropylideneketene, gives ground-state pro-
padiene at temperatures as low as 15 K.16
With the aim of preparing “push-pull” substituted
cumulated trienes,17 we have studied the addition of
dihalocarbenes to allenic phosphine oxides followed by
reaction of the products with BuLi.18 Allenic phosphine
oxides 3 are easily prepared by the method of Boisselle19
(reaction of propargylic alcohols 1 with diarylphosphine
chlorides 2).20,21
Resu lts
In general, the addition to the allenes 3 of dibromocar-
bene, dichlorocarbene,22 or bromofluorocarbene,23 gener-
ated by phase transfer catalysis, leads to alkylidene(di-
halocyclopropyl)phosphine oxides 4 (Scheme 1).
For 3a R-3d R, the addition of the dihalocarbene occurs
on the double bond remote from the phosphine oxide
group (allylic position) to give 4, 5a R, and 6bR (isolated
product, 46-56% yield). This regioselectivity is inde-
pendent of the nature of X. The configurations were
assigned on the basis of the 3J C-P coupling constants. The
only stereoisomer formed has the CX2 group trans to the
Ph2PO one; this is shown by the fact that J PC(X2) is larger
(14) The ring opening of diphenylcyclopropylidene gave rise to
optically active 1,3-diphenylallene, but it was further pointed out that
the cause for the retention of dissymmetry is dominated and probably
limited to a steric effect, see: J ones, W. N.; Krause, D. L. J . Am. Chem.
Soc. 1971, 93, 551-553.
than J PC(R R ) [J PC(X2) ) 22-24 Hz; J PC(R R ) ) 6-10 Hz].24
With 3fR, no addition occurred at all, the allene being
recovered unchanged. In contrast, with 3eR, addition of
the dihalocarbene occurred at the double bond adjacent
to the phosphine oxide forming 4eR. Attempted addition
of difluorocarbene (generated by phase transfer catalysis
from dibromomethane and dibromodifluoromethane)25 to
3a R gave rise to a very unusual reaction with the
isolation of bromoallene 7a R.26 Formally this arises from
bromination of the carbanion generated by removal of the
proton R to the phosphine oxide group.
2
3
2
3
(15) This isomerization of singlet cyclopropylidene to allene has been
the subject of several theoretical investigations: method, activation
energy (kcal mol-1), exoergicity (kcal mol-1), respectively. (a) MINDO/
2, 13.7, 40: Bodor, N.; Dewar, M. J . S.; Maksic, Z. B. J . Am. Chem.
Soc. 1973, 95, 5245-5249. (b) Simplex-INDO, 72, 25: Dillon, P. W.;
Underwood, G. R. J . Am. Chem. Soc. 1977, 99, 2435-2446. (c) 4-31G,
18.2, 74.2: Pasto, D. J .; Haley, M.; Chipman, D. M. J . Am. Chem. Soc.
1978, 100, 5272-5278. (d) 4-31G, 11, 62.6: Honjou, N.; Pacansky, J .;
Yoshimine, M. J . Am. Chem. Soc. 1984, 106, 5361-5363; 1985, 107,
5332-5341. (e) MP3/6-31G**, 11.5, 64.6: Rauk, A.; Bouma, W. J .;
Radom, L. J . Am. Chem. Soc. 1985, 107, 3780-3786. (f) STO-3G, 14,
65: Valtazanos, P.; Elbert, S. T.; Ruedenberg, K. J . Am. Chem. Soc.
1986, 108, 3147-3149. (g) FORS, 14, 65: Valtazanos, P.; Elbert, S.
T.; Xantheas, S.; Ruedenberg, K. Theor. Chim. Acta 1991, 78, 287-
326. See also: Valtazanos, P.; Ruedenberg, K. Theor. Chim. Acta 1991,
78, 397-416.
Each of the dibromocyclopropanes 4aR-4dR was treated
with BuLi (THF, -90 to 0 °C). For 4a R, the reaction gave
rise to the enyne 8 (35% yield), resulting from R-lithiation
followed by opening of the cyclopropane as shown.
(16) Monnier, M.; Allouche, A.; Verlaque, P.; Aycard, J . P. J . Phys.
Chem. 1995, 99, 5977-5985.
(17) (a) For synthesis of donor-acceptor allenes, see: Saalfrank, R.
W. Isr. J . Chem. 1985, 26, 181-190. (b) For preparation of cumulative
hosts, see: Weber, E.; Seichter, W.; Wang, R.-J .; Mak, T. C. W. Bull.
Chem. Soc. J pn. 1991, 64, 659-667.
(18) Santelli-Rouvier, C.; Santelli, M. Tetrahedron Lett. 1992, 33,
7843-7844.
(19) (a) Boisselle, A. P.; Meinhardt, N. A. J . Org. Chem. 1962, 27,
1828-1833. (b) Khusainova, N. G.; Pudovik, A. N. Russ. Chem. Rev.
1987, 56, 564-578.
(20) Clayden, J .; Warren, S. Angew. Chem., Int. Ed. Engl. 1996, 35,
241-270.
(21) The anions of allenic phosphine oxide are known precursors
for cumulatrienes; see: (a) Cadiot, P.; Chodkiewicz, W.; Borecka, B.;
Charrier, C.; Simonnin, M.-P. Chem. Abstr. 1967, 67, 116923r. (b)
Macomber, R. S.; Hemling, T. C. Isr. J . Chem. 1985, 26, 136-139. (c)
Saito, I.; Yamaguchi, K.; Nagata, R.; Murahashi, E. Tetrahedron Lett.
1990, 31, 7469-7472.
(22) Weber, W. P.; Gokel, G. W. Phase Transfer Catalysis in Organic
Synthesis; Springer-Verlag: New York, 1977; pp 18-43 and 58-62.
(23) Weyerstahl, P.; Blume, G.; Mu¨ller, C. Tetrahedron Lett. 1971,
3869-3872.
Compounds 4cR and 4d R gave the cumulated triene-
phosphine oxides 10a and 10b, respectively, in moderate
(24) Albright, T. A.; Freeman, W. J .; Schweizer, E. E. J . Am. Chem.
Soc. 1975, 97, 2946-2950.
(25) Balcerzak, P.; Fedorynski, M.; J onczyk, A. J . Chem. Soc., Chem.
Commun. 1991, 826-827.

Cumulated Trienephosphine Oxides
J . Org. Chem., Vol. 62, No. 26, 1997 9041
Sch em e 2
Sch em e 3
F igu r e 1. ORTEP plot of 14δ.
most highly alkylated olefins.30 Steric effects in their
cycloaddition with olefins are known to be small. Nev-
ertheless, rate-retarding effects have been observed with
double bonds which are substituted by bulky groups.31
Consequently, the lack of reactivity of 3fR may reason-
ably be attributed to steric hindrance. According to FMO
theory, the favored approach of a carbene to an alkene
is determined primarily by the interaction of the empty
2p orbital of the carbene with the olefinic π orbital. In
line with their observed electrophilic character, calcula-
tions show that attack of the carbene should occur
preferentially at the atom with the larger coefficient in
the olefinic π orbital.32 Previous results have shown that
dibromocarbene adds to allenes exclusively at the more
substituted double bond.33 In this study, with the excep-
tion of 3eR, addition occurred on the C(1)-C(2) double
bond, which might be expected to be the more electron
rich. Table 1 presents HOMO coefficients and energies
of these allenic phosphine oxides as obtained by semiem-
pirical calculations (AM134 and PM335 methods). We note
that for 3eR, which reacted at the C(2)-C(3) double bond,
AM1 and PM3 results indicate, as expected, a larger
coefficient on C(1) than on C(3). It appears, therefore,
that the steric effect outweighs the electronic difference.
For the allenic phosphine oxides 3bR and 3d R, the
calculations confirmed the larger coefficient of the C(1)-
C(2) double bond, and this is combined with a low
polarization (HOMO, coeff. C(1)/coeff. C(2) ) 0.96-
1.22).36 Further, the calculations show that C(3) bears
a significant negative charge and hence would indicate
yield (40-45%);27 10a was produced as a mixture of
isomers (Scheme 2).28
In contrast, a spectacular result is observed with 4bR-
bδ. The only products are the spiropentanes 14R-δ, each
isolated as a single stereoisomer (Scheme 3). The forma-
tion of 14 must result from the bimolecular addition of
the intermediate alkylidenecyclopropylidene 12 (or its
corresponding carbenoid 11) to the γ,δ-double bond of the
trienic phosphine oxide 13.
The stereochemistry of 14δ (Figure 1) was determined
by X-ray analysis and showed that if the allenic moiety
has the configuration S*, the spiro carbon atom has the
same configuration; further, the ethylenic double bond
has the E geometry. The two diphenylphosphine oxide
groups are present in a transoid orientation.29
Discu ssion
Regioselectivity of th e Dih a loca r ben e Ad d ition
to Allen ic P h osp h in e Oxid es. Dibromo- and dichlo-
rocarbene have been found to behave as electrophiles
toward simple alkenes, reacting most rapidly with the
(26) (a) Berlan, J .; Capmau, M.-L.; Chodkiewicz, W. C. R. Se´ances
Acad. Sci. 1971, 273, 1107-1110. (b) Berlan, J .; Capmau, M.-L.;
Chodkiewicz, W. Bull. Soc. Chim. Fr. 1975, 2259-2265.
(30) (a) Moss, R. A. Acc. Chem. Res. 1980, 13, 58-64. (b) Rondan,
N. G.; Houk, K. N.; Moss, R. A. J . Am. Chem. Soc. 1980, 102, 1770-
1776.
(31) Giese, B.; Lee, W. B.; Stiehl, C. Tetrahedron Lett. 1983, 24, 881-
884.
(32) Fleming, I. Frontier Orbitals and Organic Chemical Reactions;
Wiley: London, 1976.
(33) (a) Ball, W. J .; Landor, S. R. Proc. Chem. Soc. 1961, 246. (b)
Be´zaguet, A. C. R. Acad. Sci., Paris 1962, 257, 3371-3373. (c) Rahman,
W.; Kuivila, H. G. J . Org. Chem. 1966, 31, 772-776. (d) Landor, S. R.
The Chemistry of the Allenes; Academic Press: London, 1982; Vol. 2,
pp 351-360. (e) Schuster, H. E.; Coppola, G. M. Allenes in Organic
Synthesis; Wiley-Interscience: New York, 1984.
(34) Dewar, M. J . S.; Zoebisch, E. G.; Healy, E. F.; Steward, J . P. P.
J . Am. Chem. Soc. 1985, 107, 3902-3909.
(35) Stewart, J . J . P. J . Comput. Chem. 1989, 10, 209-220 and 221-
264.
(27) Concerning the addition of dihalocarbenes to allenes and
conversion of the resulting methylenedihalocyclopropanes into trienic
cumulenes, see: (a) Skattebol, L. Tetrahedron Lett. 1963, 2175-2179.
(b) Ball, W. J .; Landor, S. R.; Punja, N. J . Chem. Soc. C 1967, 194-
197. (c) Dewar, M. J . S.; Fonken, G. J .; Kirschner, S.; Minter, S. E. J .
Am. Chem. Soc. 1975, 97, 6750-6753. (d) Bee, L. K.; Beeby, J .; Everett,
J . W.; Garratt, P. J . J . Org. Chem. 1975, 40, 2212-2214. (e) Yakush-
kina, N. I.; Bolesov, I. G. Zh. Org. Khim. 1979, 15, 311-314. For the
synthesis of strained cyclic cumulated trienes, see: (f) Moore, W. R.;
Ozretich, T. M. Tetrahedron Lett. 1967, 3205-3207. (g) Angus, R. O.,
J r.; J ohnson, R. P. J . Org. Chem. 1984, 49, 2880-2883. For a review,
see: J ohnson, R. P. Chem. Rev. (Washington, D.C.) 1989, 89, 1111-
1124.
(28) Roth, W. R.; Exner, H.-D. Chem. Ber. 1976, 109, 1158-1162.
(29) Optimized PM3 calculations give bond lengths and angles which
are close to the experimental values, the main discrepancies concerning
the C-P bond lengths.
(36) For comprehensive discussions concerning the effects of orbital
polarization in the carbene addition to olefins, see: Fox, D. P.; Stang,
P. J .; Apeloig, Y.; Karni, M. J . Am. Chem. Soc. 1986, 108, 750-756.

9042 J . Org. Chem., Vol. 62, No. 26, 1997
Santelli-Rouvier et al.
Ta ble 1. F MO En er gies, Coefficien ts, a n d Op tim ized Bon d Len gth sa of Cu m u la ted Dien e- a n d Tr ien ep h osp h in e Oxid es
allenic phosphine oxidesb
cumulated trienesc
cumulated trienephosphine oxidese
energy
∆Hf (kcal/mol), 3bR: 29.0;f 3.6g
3d R: 85.5;f 63.9g
energy (au), 20a : -154.21067d,h
20b: -232.58480;d ZPE (kcal/mol):
70.6;d,i -229.29887j
∆Hf (kcal/mol), 10b: 116.3;f 92.1g
13R: 59.7;f 32.3;g -711262.26j
3eR: 102.0;f 73.6g
HOMO, eV
LUMO, eV
HOMO coeff
3bR: -9.157;f -9.659g
3d r: -9.180;f -9.545g
3er: -8.845;f -9.016g
3br: 0.069;f -0.174g
3d r: 0.036;f -0.188g
3er: -0.309;f -0.438g
3br: C(1) ) -0.44; C(2) ) -0.36;
C(3) ) 0.32f
20a : -9.007d
10b: -8.866;f -9.076g
20b: -8.363;d -6.738j
13r: -8.801;f -9.152;g -5.776j
20a : 2.578d
10b: -0.572;f -0.912g
20b: 2.933;d 5.931j
13r: -0.532;f -0.854;g 5.477j
20a : C(1) ) -C(4) ) 0.55;
C(2) ) -C(3) ) 0.39d
10b: C(1) ) -0.50; C(2) ) -0.39;
C(3) ) 0.34; C(4) ) 0.53f
3d r: C(1) ) -0.50; C(2) ) -0.44;
20b: C(1) ) -0.56; C(2) ) -0.48;
10b: C(1) ) -0.44; C(2) ) -0.41;
C(3) ) 0.33f
C(3) ) 0.37; C(4) ) 0.59d
C(3) ) 0.27; C(4) ) 0.52g
3er: C(1) ) -0.36; C(2) ) -0.36;
C(3) ) 0.25f
13r: C(1) ) -0.44; C(2) ) -0.35;
C(3) ) 0.29; C(4) ) 0.46f
13r: C(1) ) -0.41; C(2) ) -0.36;
C(3) ) 0.26; C(4) ) 0.47g
LUMO coeff
3br: C(1) ) 0.07; C(2) ) -0.04;
C(3) ) -0.07f
20a : C(1) ) C(4) ) -0.67;
C(2) ) C(3) ) 0.46d
10b: C(1) ) -0.56; C(2) ) 0.35;
C(3) ) 0.39; C(4) ) -0.52f
3d r: C(1) ) 0.08; C(2) ) -0.07;
20b: C(1) ) -0.78; C(2) ) 0.48;
10b: C(1) ) 0.56; C(2) ) -0.32;
C(3) ) -0.06f
C(3) ) 0.79; C(4) ) -0.76d
C(3) ) -0.42; C(4) ) 0.49g
3er: C(1) ) 0.28; C(2) ) -0.37;
C(3) ) -0.05f
13r: C(1) ) -0.49; C(2) ) 0.30;
C(3) ) 0.34; C(4) ) -0.46f
13r: C(1) ) 0.50; C(2) ) -0.28;
C(3) ) -0.37; C(4) ) 0.43g
net charges
3br: C(1) ) -0.078; C(2) ) -0.139;
C(3) ) -0.429f
20a : C(1) ) C(4) ) -0.38;
C(2) ) C(3) ) 0.07d
10b: C(1) ) 0.075; C(2) ) -0.178;
C(3) ) -0.037; C(4) ) -0.431f
10b: C(1) ) 0.108; C(2) ) -0.197;
C(3) ) -0.029; C(4) ) -0.793g
13r: C(1) ) 0.026; C(2) ) -0.195;
C(3) ) -0.031; C(4) ) -0.439f
13r: C(1) ) 0.044; C(2) ) -0.196;
C(3) ) 0.027; C(4) ) -0.791g
3d r: C(1) ) -0.020; C(2) ) -0.124;
20b: C(1) ) -0.11; C(2) 0.08;
C(3) ) -0.428f
C(3) ) 0.03; C(4) ) -0.40d
3er: C(1) ) -0.012; C(2) ) -0.071;
C(3) ) -0.481f
distances
C(1)-C(2)
3br: 1.310;f 1.309g
3d r: 1.312;f 1.313g
3er: 1.317;f 1.318g
3br: 1.300;f 1.302g
3d r: 1.300;f 1.302g
3er: 1.292;f 1.293g
20a : 1.302d
10b: 1.316;f 1.318g
20b: 1.307;d 1.301j
13r: 1.315;f 1.315;g 1.302j
C(2)-C(3)
20a : 1.264d
10b: 1.264;f 1.260g
20b: 1.264;d 1.254j
13r: 1.263;f 1.260;g 1.255j
C(3)-C(4)
20b: 1.304;d 1.297j
10b: 1.308;f 1.309g
13r: 1.308;f 1.309;g 1.297j
Bond lengths are expressed in angstroms. Atom numbering is as in Scheme 1. c Atom numbering is as in Scheme 4. 6-31G** level,
a
b
d
estimation of the correlation energy changes by Møller-Plesset perturbation theory truncated to second order (MP2). e Atom numbering
g
h
i
is as in Schemes 2 and 3. f Semiempirical PM3 study. Semiempirical AM1 study. See ref 37. Zero-point energies (ZPEs) are scaled by
j
0.90, see ref 47. MP2/STO-3G level.
that the regioselectivity of the dihalocarbene addition
does not involve a charge effect. In other words, the
attack of the alkene on the carbene is controlled by FMO
factors and not by Coulombic ones. Finally, we propose
that the high facial selectivity observed arises from steric
repulsion between the bulky diphenylphosphine oxide
group and the carbenic carbon atom.
with a greater reactivity of the C(1)-C(2) double bond
of the triene 13. Despite the fact that detailed ab initio
analyses for the energy surface of the ring opening of
cyclopropylidene to allene are in good agreement with
other reliable theoretical data, it remains true that
calculations have not so far reproduced the experimental
observations.15g,39 The opening of 11 (or 12) will be
dependent on its geometry. Comparison shows that the
lengths of the C-C bonds in the ring of methylenecyclo-
propane are significantly different from those of cyclo-
propane. In methylenecyclopropane 22, the bond oppo-
site the ethylenic carbon, i.e., the C(1)-C(2) bond is
lengthened (1.541 Å)40 relative to cyclopropane 21 itself
(1.514 Å)41 whereas the adjacent bond C(1)-C(3) is
shortened (1.457 Å). This effect corresponds to a weak-
ening of the former (by about 6-8 kcal/mol) and a
strengthening of the latter bond. The optimized geom-
F or m a tion of Ad d u cts 14 a n d th e Ster eoselectiv-
ity in Ad d ition . The reaction of alkylidenedibromocy-
clopropanes with alkyllithiums is known to lead to the
corresponding cumulated trienes, and this observation
was confirmed by the formation of 10a and 10b.27,38 The
dramatic change observed in the case of 4bR-δ was
unexpected and striking. In examining reasons for this
result we considered that they may, at least in principle,
be found in the greater stabilility of the carbenoid 11 (or
the alkylidenecyclopropylidene 12) and also be associated
(37) Liang, C.; Allen, L. C. J . Am. Chem. Soc. 1991, 113, 1873-
1878.
(39) Calculations reveal a sudden change in energy and/or a
geometric variable, corresponding to a small increase in the parameter
in question (“catastrophic collapse”), see ref 15b.
(40) Laurie, V. W.; Stigliani, W. M. J . Am. Chem. Soc. 1970, 92,
1485-1488.
(41) J ones, W. J .; Stoicheff, B. P. Can. J . Phys. 1964, 42, 2259-
2263.
(38) Reactions of butatrienes with dichlorocarbene yield the monoad-
dition products on C(1)-C(2) double bond and pentatetraenes are
formed with methyllithium: Karich, G.; J ochims, J . C. Chem. Ber.
1977, 110, 2680-2694. See also: Yakushkina, N. I.; Bolesov, I. G. Zh.
Org. Khim. 1979, 15, 311-314.

Cumulated Trienephosphine Oxides
J . Org. Chem., Vol. 62, No. 26, 1997 9043
Ta ble 2. Op tim ized En er gies a n d Bon d Len gth s a n d An glesa of Ca r ben oid s 24a , 24b, a n d 11r Ca lcu la ted Usin g th e a b
In itio Mp 2/Sto-3Gb a n d Com p a r ison of Geom etr ica l Da ta w ith 22 a n d 23c
24a
24b
11r
22d
23e
24a
24b
11r
22
23
energy (au)
LUMO (eV)
HOMO (eV)
net charges
C(1)
C(2)
C(3)
C(4)
Br
Li
P
O
-2704.1079 -2782.25538 -3686.4349
angles
C(1)-C(2)-C(3)
C(2)-C(1)-C(3)
C(1)-C(3)-C(2)
Li-C(2)-C(1)
Li-C(2)-C(3)
R
Br-C(2)-C(1)
Br-C(2)-C(3)
â
Br-C(2)-Li
C(1)-C(3)-C(4)
C(2)-C(3)-C(4)
C(3)-C(4)-C(7)
C(3)-C(4)-P
C(5)-C(1)-C(6)
2.798
2.888
2.774
58.8
58.5
62.7
149.8
150.7
175.3
113.0
112.5
116.4
68.2
59.0
58.2
62.8
149.8
150.1
174.0
115.8
113.7
118.8
67.1
59.2
58.3
62.5
58.1
63.5
57.7
58.8
63.6
-6.695
-6.511
-5.612
-0.157
-0.039
-0.022
-0.139
-0.009
0.095
0.002
0.004
150.0
149.6
173.8
115.9
113.8
118.9
67.3
-0.048
-0.029
-0.143
-0.005
0.080
-0.050
-0.042
-0.151
-0.007
0.086
0.883
-0.522
148.4
148.8
148.6
148.5
153.1
144.4
120.9
126.8
112.7
148.2 150.9
145.5
bond lengths
C(1)-C(2) 1.533
C(2)-C(3) 1.470
C(1)-C(3) 1.476
C(3)-C(4) 1.301
C(4)-P
1.538
1.470
1.482
1.301
1.534
1.471
1.485
1.305
1.840
1.622
1.892
2.040
2.182
1.541 1.545
1.457 1.458
1.476
112.9
0.7
1.332 1.302
C(2)-C(3)-C(4)-H(7) 1.7
4.55
C(2)-C(3)-C(4)-H(8) -178.7 -179.9
P-O
C(2)-C(3)-C(4)-C(7)
1.4
-175.9
137.6
C(2)-Li
C(2)-Br
Br-Li
1.899
2.051
2.217
1.895
2.043
2.180
C(2)-C(3)-C(4)-P
C(3)-C(4)-P-O
a
b
Bond lengths and angles are expressed in angstroms and degrees, respectively. STO-3G level, estimation of the correlation energy
changes by Møller-Plesset perturbation theory truncated to second order (MP2). c Atom numbering is as in Scheme 4. From rotational
d
spectrum, see ref 40. e From X-ray crystallography, see ref 42.
Ta ble 3. Op tim ized En er gies a n d Bon d Len gth s a n d
An glesa of Cyclop r op ylid en es 15, 18a , 18b, a n d 12r
Ca lcu la ted Usin g th e a b In itio RHF /MP 2/6-31G** or
RHF /MP 2/STO-3Gb
Sch em e 4
15c
18a c
18bc
12rd
energy (au)
ZPE (kcal/mol)
LUMO (eV)
HOMO (eV)
net charges
C(1)
-116.15526 -154.11245 -232.48619 -1132.20660
36.4e
69.9f
2.4766
-9.7056
1.2890
-9.6041
1.4538
-9.2019
4.5060
-6.0218
-0.362
0.062
-0.383
0.031
-0.173
0.031
-0.046
0.033
C(2)
C(3)
C(4)
-0.042
-0.253
-0.032
-0.271
-0.119
-0.098
bond lengths
C(1)-C(2)
C(2)-C(3)
C(1)-C(3)
C(3)-C(4)
C(1)-C(4)g
C(2)-C(4)g
angles
1.495
1.478
1.535
1.438
1.445
1.317
2.684
2.613
1.531
1.446
1.448
1.317
2.694
2.615
1.553
1.480
1.467
1.312
2.708
2.646
C(1)-C(2)-C(3) 59.2
C(2)-C(1)-C(3) 60.4
C(1)-C(3)-C(2)
58.0
57.6
64.3
152.7
143.0
58.1
58.0
63.9
153.8
142.3
57.7
58.7
63.5
154.0
142.4
C(1)-C(3)-C(4)
C(2)-C(3)-C(4)
etries of carbenoids 11R, 24a , and 24b (see Table 2 and
Scheme 4) or alkylidenecyclopropylidenes 12R, 18a , and
18b (see Table 3) are similar. The changes in molecular
geometry, and hence bond energies, must exert a strong
influence on the chemical behavior of the 1-alkylidene-
2-bromo-2-lithiocyclopropanes or alkylidenecyclopropyl-
idenes. In those reactions in which ring opening takes
place, it is the C(1)-C(2) bond that should be broken
preferentially and not the C(1)-C(3) bond.42
Structures and stabilities of some carbenoids have been
calculated with 3-21G basis sets, and in particular, it
appears that LiCH2Cl has a bridged structure.43 Calcu-
lations concerning the carbenoids 11R, 24a , and 24b
a
Bond lengths and angles are expressed in angstroms and
degrees, respectively. Atom numbering is as in Scheme 4. c 6-
31G** level, estimation of the correlation energy changes by
b
Møller-Plesset perturbation theory truncated to second order
(MP2). MP2.STO-3G. e See ref 15e. f Zero-point energies (ZPEs)
d
g
are scaled by 0.90, see ref 47. Distance between nonbonded
atoms.
(Table 2) reveal a rehybridization at the carbenoid carbon
atom with an increase in the s character of the C-Li bond
and in the p character of the C-Br bond (for 11R, R )
173.8° and â ) 118.9° instead of 123.2° in methylene-
cyclopropane).5d,44,45 Furthermore, the C(2)-Br distance
of 2.04 Å is distinctly elongated as anticipated and is
about 0.13 Å longer than the C-Br bond in gem-
dibromocyclopropanes.46 Although the presence of the
(42) In addition, the C(1)-C(3)-C(4) and C(2)-C(3)-C(4) angles in
the carbenes 18a , 18b or carbenoids 11R are 152.7, 153.8, 153.1° and
143.0, 142.3, 144.4°, respectively. Thus the exocyclic carbon is displaced
from the plane perpendicular to the ring and bissecting the C(1)-C(3)-
C(2) angle so as to be closer to C(2). Similar molecular distortions were
revealed in the structure determined by X-ray crystallography of
methylenecyclopropane-2-carboxamide, see: Van Derveer, D. G.; Bald-
win, J . E.; Parker, D. W. J . Org. Chem. 1987, 52, 1173-1174.
(43) Schleyer, P. v. R.; Clark, T.; Kos, A. J .; Spitznagel, G. W.; Rohde,
C.; Arad, D.; Houk, K. N.; Rondan, N. G. J . Am. Chem. Soc. 1984, 106,
6467-6475.
(44) In methylenecyclopropane, the value of the H-C-H (ring) angle
is 113.5 ( 1°, see ref 40.

9044 J . Org. Chem., Vol. 62, No. 26, 1997
Santelli-Rouvier et al.
Ta ble 4. Exoer gicity of th e Con ver sion of
Cyclop r op ylid en es to Cu m u len es
Sch em e 5
cyclopropylidene
∆Hf or energy
(kcal/mol)
cumulene
∆Hf or energy exoergicity
(kcal/mol)
method
PM3
AM1
MP2/6-31G**
(kcal/mol)
15
17
46.98
46.05
-72954.49
20a
114.36
120.97
-72888.53
18a
67.38
74.92
65.96a
PM3
AM1
MP2/6-31G**
141.45
148.81
-96707.04
18b
78.54
75.99
-96768.67
20b
62.91
72.82
61.63
PM3
AM1
MP2/6-31G**
128.83
138.32
-145887.31
12r
131.70
118.65
-711188.87
19
59.69
59.13
-145949.19
13r
59.76
32.29
-711262.32
10b
69.14
79.19
61.88
PM3
AM1
MP2/STO-3G
71.94
86.36
73.45
PM3
AM1
189.09
178.93
116.33
92.15
72.76
86.78
a
See ref 15f.
Ta ble 5. Ca lcu la ted En er gies for th e F or m a tion of
Cyclop r op ylid en es a n d LiBr fr om Ca r ben oid s a t th e
MP 2/STO-3G Level
Sch em e 6
carbenoid
energy (kcal/mol)
cyclopropylidene
energy (kcal/mol)
∆E
(kcal/mol)
16
15
-1673374.43
-71847.80
57.44
57.63
58.62
58.09
24a
18a
-1696853.56
24b
-95326.74
18b
-1745342.68
-143814.87
11r
12r
-2312716.15
-711188.87
corresponding cumulene (∆E ≈ 0.5 eV). These effects are
more important for 13R. Recalling that the cycloaddi-
tions of carbenes (or carbenoids) to alkenes are LU(car-
bene)-HO(alkene) controlled (the “electrophilic term”),32,48
we note that for the cumulated trienephosphine oxides
and the phosphine oxide substituted carbenoids, the
interaction LU(triene)-HO(carbenoid) (the “nucleophilic
term”) becomes an important contributor which can
explain the increased rate of cycloaddition. Moreover,
at the STO-3G level the HOMO of 13R is essentially a
C(2)-C(3) π-orbital interacting with the PdO group
orbital (energy, -5.776 eV, coeff. (pz) C(1), 0.02; C(2),
-0.20; C(3), -0.11; C(4), 0.23; O, 0.782), the π-orbital of
the 1,3-diene is the HOMO-2 (energy, -6.727 eV, coeff.
(py) C(1), 0.430; C(2), 0.325; C(3), -0.295; C(4), -0.457).
In contrast, the LUMO is the π*-orbital of the 1,3-diene,
as expected (energy, 5.477 eV, coeff. (py) C(1), -0.534;
C(2), 0.330; C(3), 0.378; C(4), -0.516).
The conversion from carbenoid to carbene results in a
decrease in the energy of the LUMO of 12R relative to
11R, consequently the interaction LU(carbene)-HO(tri-
ene) becomes more important as that between LU(triene)
and HO(carbene). This would also favor an increase in
the rate of addition of carbene.
In considering the stereoselectivity of the addition of
11 (or 12) to 13, it is obvious that it cannot be accounted
for by an “open” transition state. Consequently, we favor
the “compact” transition state depicted in Scheme 6 as
the most probable. Such a transition state keeps the
bulky diarylphosphinyl groups apart, while allowing
diphenylphosphine oxide group does not modify the
charges or the energy of the LUMO, it leads, significantly,
to a higher level for the HOMO (∆E ≈ 0.9 eV). The
presence of the diphenylphosphine oxide group also
increases the exoergicity of the conversion from alkyli-
denecyclopropylidene to butatriene (Table 4).
The formation of cyclopropylidenes by elimination of
LiBr from the carbenoids is an endothermic process with
an energy change in the range 57.4-58.6 kcal/mol at the
MP2/STO-3G level (energy of LiBr: -1 601 469.19 kcal/
mol) (Table 5).
In considering our proposal, that the reactivity of the
trienes 13 may be enhanced, we have carried out ab initio
and PM3 or AM1 molecular orbital calculations for
butatriene, cumulated diene and trienephosphine oxides
(Table 1). These reveal a relatively high HOMO energy
and a particularly low LUMO energy for trienephosphine
oxides 10b and 13R (Scheme 5). Thus the introduction
of the diphenylphosphine oxide group causes a significant
lowering of the LUMO energy level compared with the
(45) A rehybridization at the alkylidene carbenoid carbon atom was
confirmed by X-ray crystallographic analysis of the 1-chloro-1-lithio-
2,2-diphenylethene, see: Boche, G.; Marsch, M.; Mu¨ller, A.; Harms,
K. Angew. Chem., Int. Ed. Engl. 1993, 32, 1032-1033. See also,
Maercker, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 1023-1025.
(46) It should be noted that 13C NMR evidence suggests a weak,
highly polarized C-Br bond in cyclopropylcarbenoids; see ref 5. The
carbon-bromine bond length value in gem-dibromocyclopropanes is
1.91 ( 0.01 Å. See: Paquette, L. A.; Fristad, W. E.; Schuman, C. A.;
Beno, M. A.; Christoph, G. G. J . Am. Chem. Soc. 1979, 101, 4645-
4655.
(47) Hehre, W. J .; Radom, L.; Schleyer, P. v. R.; Pople, J . A. Ab Initio
Molecular Orbital Theory; J ohn Wiley & Sons: New York, 1986; p 251.
(48) Moss, R. A.; Perez, L. A.; Wlostowska, J .; Guo, W.; Krogh-
J espersen, K. J . Org. Chem. 1982, 47, 4177-4180.

Cumulated Trienephosphine Oxides
J . Org. Chem., Vol. 62, No. 26, 1997 9045
) 7.2 Hz) (s), 132.6 (d, J PC ) 10.4 Hz) (d), 128.4 (d, J PC ) 12.6
Hz) (d), 128.2 (d, J PC ) 3.3 Hz) (s), 97.4 (d, J PC ) 14.5 Hz) (s),
90.2 (d, J PC ) 105.7 Hz) (s), 19.1 (d, J PC ) 5.9 Hz) (q), 13.9 (d,
J PC ) 8.7 Hz) (q); 31P NMR (CDCl3) δ 29.7; MS m/z 355 (18),
352 (44), 350 (66), 269 (100), 235 (17), 170 (13), 159 (21), 152
(14); HRMS calcd for C18H17OP35Cl2 350.03940, found 350.0402.
4-Meth yl-2-[bis(4-br om op h en yl)p h osp h in yl]-2,3-p en ta -
d ien e (3bγ). Reaction of 1b and 2γ following the general
nucleophilic attack of the anion onto the triene, followed
by expulsion of the bromide, and also permitting favor-
able secondary FMO interactions. These secondary
interactions are shown more clearly in the carbene- or
carbenoid-triene pictures in Scheme 5.
This interaction of LU(triene) with HO(carbenoid) can
be regarded as a nucleophilic addition of the carbanion
part of 11 to 13 leading to a phosphorus-stabilized
propargyl anion.49 Such an interaction cannot occur in
the addition of carbenoids to simple alkenes.
procedure gave 3bγ: 72% yield; IR 1967 cm-1 1H NMR
;
(CDCl3) δ 7.57-7.42 (m, 8H), 1.82 (d, J ) 12.0 Hz, 3H), 1.39
(d, J ) 6.5 Hz, 6H); 13C NMR (CDCl3) δ 208.3 (s), 132.9 (d, J PC
) 10.0 Hz) (d), 131.6 (d, J PC ) 12.0 Hz) (d), 130.9 (d, J PC
)
105.0 Hz) (s), 97.6 (d, J PC ) 14.6 Hz) (s), 90.3 (d, J PC ) 105.0
Hz) (s), 19.3 (d, J PC ) 5.8 Hz) (q), 14.1 (d, J PC ) 8.1 Hz) (q).
Anal. Calcd for C18H17Br2OP: C, 49.12; H, 3.89. Found: C,
49.24; H, 3.92.
Con clu sion
In conclusion, the formation of the spiro compounds
14 probably results from a combination of factors: (a)
the slow rate of opening of the alkylidenecyclopropane
compounds 11 (or 12), (b) the presence of the diphenyl-
phosphine oxide group which increases the energy of the
HOMO of 11 (or 12), (c) the presence of the diphenyl-
phosphine oxide group which lowers the energy of the
LUMO of 13, and (d) the stereoselectivity of the addition
being controlled by the stabilizing secondary orbital
interactions in the transition state.
4-Meth yl-2-[bis(4-ter t-bu tylph en yl)ph osph in yl]-2,3-pen -
ta d ien e (3bδ). Reaction of 1b and 2δ following the general
1
procedure gave 3bδ: 68%; IR 1965 cm-1; H NMR (CDCl3) δ
7.59-7.49 (m, 4m), 7.38-7.33 (m, 4H), 1.79 (d, J PC ) 11.8 Hz,
3H), 1.29 (d, J PC ) 6.4 Hz, 6H), 1.22 (s, 9H); 13C NMR (CDCl3)
δ 207.9 (d, J PC ) 6.8 Hz) (s), 154.7 (d, J PC ) 2.8 Hz) (s), 131.3
(d, J PC ) 9.8 Hz) (d), 128.8 (d, J PC ) 106.0 Hz) (s), 125.1 (d,
J PC ) 12.0 Hz) (d), 96.7 (d, J PC ) 14.2 Hz) (s), 91.0 (d, J PC
)
103.0 Hz) (s), 34.8 (s), 31.0 (q), 19.2 (d, J PC ) 6.2 Hz) (q), 14.0
(d, J PC ) 8.1 Hz) (q). Anal. Calcd for C26H35OP: C, 79.15; H,
8.94. Found: C, 79.24; H, 8.89.
4-Cyclop r op yl-2-(d ip h e n ylp h osp h in yl)-2,3-p e n t a d i-
en e (3cr). Reaction of 1c and 2R following the general
procedure gave 3cR: 67% yield; IR 1952, 1440 cm-1; 1H NMR
(CDCl3) δ 7.7 (m, 4H), 7.45 (m, 6H), 1.88 (d, J ) 11.7 Hz, 3H),
1.45 (d, J ) 6.2 Hz, 3H), 0.93 (m, 1H), 0.45 (m, 2H), 0.08 (m,
1H), -0.32 (m, 1H); 13C NMR (CDCl3) δ 207.1 (s), 131.0-129.0
(d), 103.7 (d, J PC ) 14.0 Hz) (s), 93.0 (d, J PC ) 103.7 Hz) (s),
16.7 (d, J PC ) 5.9 Hz) (d or q), 14.3 (d, J PC ) 8.3 Hz) (d or q),
12.8 (d, J PC ) 6.5 Hz) (d or q), 5.2 (t); 31P NMR (CDCl3) δ 30.8.
Anal. Calcd for C20H21OP: C, 77.90; H, 6.86. Found: C, 77.98;
H, 6.90.
1,1-Dicyclop r op yl-3-(d ip h en ylp h osp h in yl)-1,2-bu ta d i-
en e (3d r). Reaction of 1d and 2R following the general
procedure gave 3d R: 68% yield, mp 192-193 °C; IR 1955,
1440, 1195 cm-1; 1H NMR (CDCl3) δ 7.9-7.6 (m, 4H), 7.45 (m,
6H), 1.95 (d, J ) 12.0 Hz, 3H), 1.05 (m, 2H), 0.53 (m, 4H), 0.3
(m, 2H), -0.1 (m, 2H); 13C NMR (CDCl3) δ 207.0 (d, J PC ) 7.4
Hz) (s), 131.7 (d, J PC ) 105.0 Hz) (s), 131.6 (d), 131.4 (d), 131.9
(d), 128.0 (d, J PC ) 12.3 Hz) (d), 111.4 (d, J PC ) 13.5 Hz) (s),
95.3 (d, J PC ) 103.5 Hz) (s), 14.6 (d, J PC ) 8.5 Hz) (d or q),
11.2 (d, J PC ) 6.2 Hz) (d or q), 5.3 (d, J PC ) 2.2 Hz) (t); 31P
NMR (CDCl3) δ 16.4. Anal. Calcd for C22H23OP: C, 79.02;
H, 6.93. Found: C, 79.12; H, 6.87.
Exp er im en ta l Section
Gen er a l. All reactions were run under argon in oven-dried
glassware. TLC was performed on silica gel 60 F254.
1H and
13C NMR spectra were recorded in CDCl3 solutions at 400, 200
and 100, 50 MHz, respectively. Diarylphosphine chlorides 2
were prepared according to the literature procedure.50
Gen er a l P r oced u r e for th e P r ep a r a tion of Allen ic
P h osp h in e Oxid es. To a stirred and cooled (0 °C) solution
of the acetylenic alcohol (20 mmol) in anhydrous ether (20 mL)
and pyridine (1.94 mL, 24 mmol) under argon was added
dropwise diarylphosphine chloride (20 mmol) in CH2Cl2 (20
mL). The stirring was maintained 1 h at 0 °C and at room
temperature overnight. The solution was then poured onto
ice and extracted with CH2Cl2, and the organic layer was dried
(MgSO4). Concentration in vacuo gave the crude product that
was subjected to flash chromatography on silica gel eluting
with ether.
3-Meth yl-1-(d ip h en ylp h osp h in yl)-1,2-bu ta d ien e (3ar).
Reaction of 1a and 2R following the general procedure gave
3a R: 75-80% yield, mp 71-72 °C;19a,51 IR 1958, 1440 cm-1
;
1H NMR (CDCl3) δ 7.73-7.62 (m, 4H), 7.43 (m, 6H), 5.61 (sept.,
J ) 3.2 Hz, 1H), 1.47 (dd J ) 6.3, 3.2 Hz, 6H); 13C NMR
(CDCl3) δ 208.6 (s), 133.1 (d, J PC ) 105.0 Hz) (s), 131.8-131.0
1,1-Dip h en yl-3-(d ip h en ylp h osp h in yl)-1,2-p r op a d ien e
(3er). Reaction of 1e and 2R following the general procedure
gave 3eR: 67% yield; mp 170-171 °C;51 IR 1942, 1460, 1440
(d), 128.5-128.1 (d), 97.6 (d, J PC ) 13.0 Hz) (s), 83.7 (d, J PC
)
107.0 Hz) (d), 18.8 (J PC ) 5.5 Hz) (q); 31P NMR (CDCl3) δ 24.90.
4-Meth yl-2-(diph en ylph osph in yl)-2,3-pen tadien e (3br).
Reaction of 1b and 2R following the general procedure gave
1
cm-1; H NMR (CDCl3) δ 7.86-7.66 (m, 5 H), 7.66-7.34 (m,
12 H), 7.15-7.11 (m, 3 H), 6.45 (d, J ) 1.5 Hz, 1H); 13C NMR
(CDCl3) δ 206.0 (s), 134.2 (d, J PC ) 33.0 Hz) (s), 131.0-128.0
(d), 111.0 (s), 88.8 (d, J PC ) 101.6 Hz) (d).
3bR, 82% yield, mp 89-90 °C; IR 1953, 1438 cm-1; H NMR
1
(CDCl3) δ 8.00-7.33 (m, 10H), 1.91 (d, J ) 12.0 Hz, 3H), 1.43
(d, J ) 7.0 Hz, 6H); 13C NMR (CDCl3) δ 207.7 (d, J PC ) 7.0
Hz) (s), 131.6 (d, J PC ) 103.0 Hz) (s), 131.0-127.0 (d), 96.7 (d,
3-Meth yl-1-p h en yl-1-(d ip h en ylp h osp h in yl)-1,2-bu ta d i-
en e (3fr). Reaction of 1f and 2R following the general
procedure gave 3fR: 52% yield; mp 125 °C;52 IR 1951, 1440
cm-1; 1H NMR (CDCl3) δ 8.1-7.2 (m, 15H), 1.5 (d, J ) 6.0 Hz,
6H); 13C NMR (CDCl3) δ 210.0 (s), 132.8 (d, J PC ) 105.0 Hz)
(s), 131.5 (d), 128.3 (d), 100.4 (d, J PC ) 103.0 Hz) (s), 100.0 (d,
J PC ) 13.6 Hz) (s), 19.0 (d, J PC ) 10.7 Hz) (q); 31P NMR (CDCl3)
δ 30.73; MS m/z 344 (99), 329 (12), 286 (13), 201 (100), 155
(24), 143 (67); HRMS calcd for C23H21OP 344.13299, found
344.1322.
Gen er a l P r oced u r e of th e Ad d ition of Dih a loca r ben e
to Allen ic P h osp h in e Oxid es 3. Allenic phosphine oxide 3
(30 mmol), bromoform or chloroform (30 mL) or dibromofluo-
romethane (10 g), triethylbenzylammonium chloride (200 mg)
were stirred at 0 °C. A solution of 50% aqueous NaOH was
added dropwise, and stirring was maintained at room tem-
J PC ) 14.5 Hz) (s), 90.4 (d, J PC ) 103.5 Hz) (s), 18.8 (d, J PC
)
6.1 Hz) (q), 13.7 (d, J PC ) 8.5 Hz) (q); 31P NMR (CDCl3) δ 32.0.
Anal. Calcd for C18H19OP: C, 76.58; H, 6.78. Found: C, 76.48;
H, 6.72.
4-Meth yl-2-[bis(4-ch lor op h en yl)p h osp h in yl]-2,3-p en ta -
d ien e (3bâ). Reaction of 1b and 2â following the general
procedure gave 3bâ: 66% yield; mp 104-106 °C; IR 1962 cm-1
;
1H NMR (CDCl3) δ 7.49-7.20 (m, 8H), 1.68 (d, J ) 12.0 Hz,
3H), 1.25 (d, J ) 6.4 Hz, 6H); 13C NMR (CDCl3) δ 208.8 (d, J PC
(49) The mechanism shown in Scheme 6 involves an intramolecular
nucleophilic substitution of a cyclopropyl bromide by a phosphorus-
stabilized propargyl carbanion. For such as nucleophilic displace-
ments, see: J ohnson, C. R.; J aniga, E. R. J . Am. Chem. Soc. 1973, 95,
7692-7700.
(50) Hunt, B. B.; Saunders, B. C. J . Chem. Soc. 1957, 2413-2414.
(51) Simonnin, M.-P.; Borecka, B. Bull. Soc. Chim. Fr. 1966, 3842-
3843.
(52) Heydt, H.; Regitz, M. J . Chem. Res. Miniprint 1978, 4248,
4270-4288.

9046 J . Org. Chem., Vol. 62, No. 26, 1997
Santelli-Rouvier et al.
perature. The addition was followed by TLC (silica gel, eluent
ether-methanol, 99/1). Aqueous NaOH was added until no
more change occurred, even if the allenic phosphine oxide
remained. The dark mixture was extracted with CH2Cl2, and
the solution was washed to neutrality, dried over SO4Mg,
concentrated in vacuo, and chromatographed on silica gel
(eluent, ether) to give 4 or 6bR.
and bromoform following the general procedure gave 4d R: 50%
yield; mp 145 °C; IR 1440 cm-1; 1H NMR (CDCl3) δ 7.66-7.46
(m, 10H), 2.02 (d, J ) 12.3 Hz, 3H), 1.27 (m, 4H), 0.60-0.30
(m, 4H), 0.17 (m, 2H); 13C NMR (CDCl3) δ 146.1 (s), 131.9 (d),
131.5 (d), 128.6 (d, J PC ) 12.2 Hz) (d), 45.9 (d, J PC ) 4.5 Hz)
(s), 31.9 (d, J PC ) 14.6 Hz) (s), 18.7 (d)(2C), 17.1 (d, J PC ) 12.8
Hz) (q), 5.50 (t)(2C), 3.03 (t)(2C). Anal. Calcd for C23H23Br2-
OP: C, 54.57; H, 4.58. Found: C, 54.50; H, 4.66.
1,1-Dib r om o-2,2-d im et h yl-3-[(d ip h en ylp h osp h in yl)-
m eth ylid en e]cyclop r op a n e (4a r). Reaction of 3a R and
bromoform following the general procedure gave 4a R: 52%
1,1-Dibr om o-2-(diph en ylm eth yliden e)-3-(diph en ylph os-
p h in yl)cyclop r op a n e (4er). Reaction of 3eR and bromoform
following the general procedure gave 4eR: 32% yield; mp 159-
yield; mp 99-100 °C; IR 1438, 1107, 1120 cm-1 1H NMR
;
1
(CDCl3) δ 8.03-7.7 (4H), 7.56 (m, 6H), 7.06 (d, J ) 20 Hz, 1H),
1.36 (s, 6H); 13C NMR (CDCl3) δ 157.2 (d, J PC ) 4.0 Hz) (s),
133.3 (d, J PC ) 105.0 Hz) (s), 132.3 (d), 131.4 (d, J PC )10.0
Hz) (d), 128.9 (d, J PC ) 13.0 Hz) (d), 117.3 (d, J PC )100.0 Hz)
(d), 35.2 (d, J PC ) 6.0 Hz) (s), 31.3 (d, J PC ) 22.0 Hz) (s), 25.2
160 °C; IR 1440 cm-1; H NMR (CDCl3) δ 7.68-7.58 (m, 3H),
7.58-7.05 (m, 13H), 7.05-6.96 (m, 4H), 3.32 (d, J ) 3.1 Hz,
1H); 13C NMR (CDCl3) δ 141.2 (s), 131.8-127.8 (d), 118.8 (s),
47.9 (d, J PC ) 2.0 Hz) (s), 36.6 (d, J PC ) 88.0 Hz) (d). Anal.
Calcd for C28H21Br2OP: C, 59.60; H, 3.75. Found: C, 59.71;
H, 3.67.
(q) (2C); 31P NMR (CDCl3) δ 20.01. Anal. Calcd for C18H17
Br2OP: C, 49.12; H, 3.89. Found: C, 49.22; H, 3.94.
-
1,1-Dich lor o-2,2-d im eth yl-3-[1-(d ip h en ylp h osp h in yl)-
eth ylid en e]cyclop r op a n e (6br). Reaction of 3bR and chlo-
roform following the general procedure gave 6bR: 56% yield;
1,1-Dibr om o-2,2-d im eth yl-3-[1-(d ip h en ylp h osp h in yl)-
eth ylid en e]cyclop r op a n e (4br). Reaction of 3bR and bro-
moform following the general procedure gave 4bR: 48% yield;
1
IR 1440 cm-1; H NMR (CDCl3) δ 7.73 (m, 10H), 2.26 (d, J )
1
mp 132 °C; IR 1440 cm-1; H NMR (CDCl3) δ 7.71-7.47 (m,
12.0 Hz, 3H), 1.13 (s, 6H); 13C NMR (CDCl3) δ 147.0 (s), 131.6
(d), 128.5 (d), 89.8 (d, J PC ) 105.0 Hz) (s), 60.2 (d, J PC ) 22.0
10H), 2.18 (d, J ) 11.8 Hz, 3H), 1.07 (s, 6H); 13C NMR (CDCl3,
100 MHz) δ 149.1 (d, J PC ) 14.0 Hz) (s), 132.4 (d), 132.0 (d,
J PC ) 10.0 Hz) (d), 128.8 (d, J PC ) 12.0 Hz) (d), 127.9 (d, J PC
) 96.0 Hz) (s), 35.9 (d, J PC ) 4.9 Hz) (s), 31.8 (d, J PC ) 21.0
Hz) (s), 25.1 (q) (2C), 16.0 (d, J PC ) 10.0 Hz) (q); 31P NMR
(CDCl3) δ 26.8; MS m/z 456 (6), 454 (16), 452 (6), 375 (27),
373 (24), 294 (33), 293 (39), 201 (100), 183 (25), 181 (19), 169
(29); HRMS calcd for C19H19OP79Br2 451.9540, found 451.9563.
1,1-Dibr om o-2-[1-[bis-(4-ch lor op h en yl)p h osp h in yl]eth -
ylid en e]-3,3-d im eth ylcyclop r op a n e (4bâ). Reaction of 3bâ
and bromoform following the general procedure gave 4bâ: 47%
yield; mp 174-175 °C; IR 1440 cm-1; 1H NMR (CDCl3) δ 7.58-
7.41 (m, 8H), 2.08 (d, J ) 12.1 Hz, 3H), 1.11 (s, 6H); 13C NMR
(CDCl3) δ 150.4 (d, J PC ) 12.0 Hz) (s), 139.2 (d, J PC ) 2.3 Hz)
(s), 133.2 (d, J PC ) 10.7 Hz) (d), 129.2 (d, J PC ) 12.7 Hz) (d),
35.9 (d, J PC ) 5.1 Hz) (s), 31.0 (d, J PC ) 21.7 Hz) (s), 25.1 (q),
15.9 (d, J PC ) 10.5 Hz) (q); 31P NMR (CDCl3) δ 24.8. Anal.
Calcd for C19H17Br2Cl2OP: C, 43.63; H, 3.28. Found: C, 43.70;
H, 3.24.
Hz) (s), 35.0 (d, J PC ) 5.0 Hz) (s), 22.0 (q) (2C), 16.4 (d, J PC
)
10.0 Hz) (q). Anal. Calcd for C19H19Cl2OP: C, 62.48; H, 5.24.
Found: C, 62.55; H, 5.18.
1-Br om o-1-flu or o-2,2-d im eth yl-3-[(d ip h en ylp h osp h in -
yl)m eth ylid en e]cyclop r op a n e (5a r). Allenic phosphine
oxide 3a R (2.6 g, 10 mmol), dibromofluoromethane (3.3 g, 16
mmol), and triethylbenzylammonium chloride (50 mg) were
stirred at room temperature. A solution of 50% aqueous NaOH
(2 g) was added dropwise. After 3 h, the mixture was extracted
with CH2Cl2, and the solution was washed to neutrality, dried
over SO4Mg, concentrated in vacuo, and chromatographed on
silica gel (eluent, ether). The yield (about 20%) was very low,
and no further attempts were done to improve it. 5a R: IR
1440 cm-1 1H NMR (CDCl3) δ 7.59 (m, 4H), 7.38 (m, 10H),
;
6.98 (d, J ) 21.6 Hz, 1H), 1.09 (br s, 6H); 13C NMR (CDCl3) δ
152.9 (s), 133.1 (d, J PC ) 1.9 Hz) (s), 132.0 (d, J PC ) 2.6 Hz)
(d), 130.9 (d, J PC ) 10.0 Hz) (d), 128.5 (d, J PC ) 12.3 Hz) (d),
118.2 (d, J PC ) 98.0 Hz) (d), 81.8 (d, J FC ) 315 Hz, d, J PC
)
1,1-Dibr om o-2-[1-[bis(4-br om op h en yl)p h osp h in yl]eth -
ylid en e]-3,3-d im eth ylcyclop r op a n e (4bγ). Reaction of 3bγ
and bromoform following the general procedure gave 4bγ: 52%
24.0 Hz) (s), 33.7 (d, J FC ) 11.8 Hz, d, J PC ) 6.8 Hz) (s), 24.0
(q), 17.9 (d, J PC ) 5.6 Hz) (q); 31P NMR (CDCl3) δ 20.0. Anal.
Calcd for C18H17BrFOP: C, 57.01; H, 4.52. Found: C, 56.86;
H, 4.61.
yield; IR 1440 cm-1
;
1H NMR (CDCl3) δ 7.64-7.60 (m, 4H),
7.51-7.41 (m, 4H), 2.09 (d, J ) 12.2 Hz, 3H), 1.13 (s, 6H); 13
NMR (CDCl3) δ 150.5 (d, J PC ) 13.5 Hz) (s), 133.3 (d, J PC
C
)
1-Br om o-1-(d ip h en ylp h osp h in yl)-3-m eth yl-1,2-bu ta d i-
en e (7a r). Phosphine oxide 3a R (2.7 g, 10 mmol), CH2Br2 (6.9
g, 40 mmol), CBr2F2 (8.4 g, 40 mmol), KOH (4.5 g, 80 mmol),
water (7.4 mL), and tetrabutylammonium sulfate (0.34 g, 1
mmol) were stirred during 24 h. After extraction with CH2Cl2,
the solution was washed to neutrality, dried over SO4Mg,
concentrated in vacuo, and chromatographed on silica gel
(eluent, ether) to give 2.1 g (60% yield) of 7a R. A similar result
was obtained when 3a R was stirred only with CBr2F2. 7a R:
10.8 Hz) (d), 132.2 (d, J PC ) 12.6 Hz) (d), 129.9 (d, J PC ) 104.0
Hz) (s), 127.8 (d, J PC ) 3.4 Hz) (s), 35.9 (d, J PC ) 5.1 Hz) (s),
31.0 (d, J PC ) 21.6 Hz) (s), 25.2 (q) (2C), 15.9 (d, J PC ) 10.4
Hz) (q). Anal. Calcd for C19H17Br4OP: C, 37.29; H, 2.80.
Found: C, 37.35; H, 2.87.
1,1-Dibr om o-2-[1-[bis(4-ter t-bu tylp h en yl)p h osp h in yl]-
eth ylid en e]-3,3-d im eth ylcyclop r op a n e (4b δ). Reaction of
3bδ and bromoform following the general procedure gave
mp 98-99 °C;26 IR 1951, 1440, 1210, 1020 cm-1 1H NMR
;
1
4bδ: 47% yield; IR 1440 cm-1; H NMR (CDCl3) δ 7.54-7.46
(CDCl3) δ 7.64-7.51 (m, 4H), 7.32-7.25 (m, 6H), 1.39 (m, 6H);
13C NMR (CDCl3) δ 206.0 (s), 131.9 (d, J PC ) 2.55 Hz) (d), 131.3
(d, J PC ) 9.7 Hz) (d), 130.4 (d, J PC ) 11.0 Hz) (d), 129.9 (d, J PC
) 110 Hz) (s), 128.0 (d, J PC ) 12.6 Hz) (d), 108.0 (d, J PC ) 9.5
Hz) (s), 79.6 (d, J PC ) 117.6 Hz) (s), 19.0 (q); 31P NMR (CDCl3)
δ 25.8; MS m/z 348 (23), 346 (23), 268 (20), 267 (100), 201 (82),
143 (68), 128 (22); HRMS calcd for C17H16OP79Br 346.01220,
found 346.0112, calcd for [M - Br]+ 267.09387, found 267.0936.
Gen er a l P r oced u r e for th e Rea ction of n -Bu tyllith iu m
w ith gem -Dibr om ocyclop r op a n es 4. To a stirred and
cooled (-90 °C) solution of gem-dibromocyclopropane 4 (2
mmol) in anhydrous THF (15 mL) under argon was added
n-BuLi (1.6 M in hexane, 1.4 mL). After 1 h, the mixture was
allowed to warm slowly to room temperature overnight. After
hydrolysis and extraction with CH2Cl2, the organic layers were
washed to neutrality and dried over SO4Mg. The solvent was
eliminated in vacuo and the crude product chromatographed
on silica gel (eluent, ether to ether-methanol, 98/2).
(m, 8H), 2.19 (d, J ) 11.7 Hz, 3H), 1.27 (s, 18H), 1.01 (s, 6H);
13C NMR (CDCl3) δ 155.7 (d, J PC ) 2.7 Hz) (s), 148.0 (d, J PC
)
12.0 Hz) (s), 131.8 (d, J PC ) 10.3 Hz) (d), 128.1 (d, J PC ) 105.7
Hz) (s), 125.7 (d, J PC ) 12.4 Hz) (d), 35.7 (d, J PC ) 4.7 Hz) (s),
35.0 (s)(2C), 32.0 (d, J PC ) 23.0 Hz) (s), 31.2 (q) (6C), 24.9 (q)
(2C), 15.9 (d, J PC ) 10.0 Hz) (q). Anal. Calcd for C27H35Br2OP:
C, 57.26; H, 6.23. Found: C, 57.18; H, 6.31.
1,1-Dib r om o-2-cyclop r op yl-2-m et h yl-3-[1-(d ip h en yl-
p h osp h in yl)eth ylid en e]cyclop r op a n e (4cr). Reaction of
3cR and bromoform following the general procedure gave
4cR: 52% yield; IR 1440 cm-1; 1H NMR (CDCl3) δ 7.5 (m, 10H),
2.10 (d, J ) 12.0 Hz, 3H), 1.4 (s, 3H), 1.4-0.2 (m, 5H); 13C
NMR (CDCl3) δ 147.9 (d, J PC ) 10.6 Hz) (s), 132.8 (d, J PC ) 8
Hz), 131-128 (d), 127.3 (d, J PC ) 64.5 Hz) (s), 40.2 (d, J PC
)
5.0 Hz) (s), 31.0 (d, J PC ) 19.8 Hz) (s), 22.3 (q), 19.1 (d), 16.1
(d, J PC ) 10.8 Hz) (q), 6.1 (t), 2.7 (t); 31P NMR (CDCl3) δ 23.93.
Anal. Calcd for C21H21Br2OP: C, 52.53; H, 4.41. Found: C,
52.61; H, 4.36.
1-(Dip h en ylp h osp h in yl)-4-m eth yl-3-p en ten -1-yn e (8).
Reaction of 4a R and n-BuLi following the general procedure
1,1-Dib r om o-2,2-d icyclop r op yl-3-[1-(d ip h e n ylp h os-
p h in yl)eth ylid en e]cyclop r op a n e (4d r). Reaction of 3d R
1
gave 8: 35% yield; IR 2140, 1435, 1200, 1115 cm-1; H NMR

Cumulated Trienephosphine Oxides
J . Org. Chem., Vol. 62, No. 26, 1997 9047
(CDCl3) δ 7.87-7.75 (m, 4H), 7.48-7.38 (m, 6H), 5.42 (br. s,
1H), 1.93 (s, 3H), 1.85 (s, 3H); 13C NMR (CDCl3) δ 157.2 (s),
135.0 (s), 132.0 (d), 131.0 (d), 128.5 (d), 104.6 (d, J PC ) 30.0
Hz) (s), 103.6 (d, J PC ) 4.0 Hz) (d), 25.3 (q), 21.9 (q). Anal.
Calcd for C18H17OP: C, 77.13; H, 6.11. Found: C, 77.07; H,
6.10.
(3S*)-(E)-2-[1-[Bis(4-ter t-bu tylp h en yl)p h osp h in yl]eth -
yliden e]-5-[(S*)-2-[bis(4-ter t-bu tylph en yl)ph osph in yl]pr op-
1-en ylid en e]-1,1,4,4-tetr a m eth ylsp ir o[2.2]p en ta n e (14δ).
Reaction of 4bδ and n-BuLi following the general procedure
gave 14δ: 58% yield; mp 130-132 °C (AcOEt-ligroin); IR
1998, 1605, 1190 cm-1; 1H NMR (CDCl3) δ 7.6-7.23 (m, 16H),
1.90 (d, J ) 11.3 Hz, 3H), 1.39 (d, J ) 11.9 Hz, 3H), 1.23 (s),
1.21 (s), 1.18 (s), 1.13 (s) (1.23 to 1.13, 39H), 0.92 (s, 3H), 0.66
(s, 6H); 13C NMR (CDCl3) δ 188.2 (d, J PC ) 9.2 Hz) (s), 155.1
(d, J PC ) 2.6 Hz) (s), 154.8 (d, J PC ) 15.0 Hz) (s), 154.6 (d, J PC
) 2.8 Hz) (s), 150.6 (d, J PC ) 14.3 Hz) (s), 131.8 (d, J PC ) 4.1
Hz) (d), 131.5 (d, J PC ) 9.6 Hz) (d), 131.4 (d, J PC ) 15.3 Hz)
(d), 129.9 (d, J PC ) 107.6 Hz) (s), 129.1 (d, J PC ) 104.5 Hz) (s),
129.0 (d, J PC ) 104 Hz) (s), 128.2 (d, J PC ) 105.9 Hz) (s), 125.3
(d, J PC ) 12.0 Hz) (d), 125.2 (d, J PC ) 12.3 Hz) (d), 117.4 (d,
2-Cyclop r op yl-5-(d ip h en ylp h osp h in yl)-2,3,4-h exa t r i-
en e (10a ). Reaction of 4cR and n-BuLi following the general
procedure gave 10a : 45% yield; IR 2061, 1441 cm-1; 1H NMR
(CDCl3) δ 7.7 (m, 4H), 7.36 (m, 6H), 2.03 (d, J ) 12.5 Hz, 3H),
1.3 (br s, 3H), 0.75 (m, 2H), 0.6 (m, 2H); 13C NMR (CDCl3) δ
(minor isomer) 167.5 (d, J PC ) 8.0 Hz) (s), 150.0 (d, J PC ) 7.0
Hz) (s), 92.7 (d, J PC ) 103.6 Hz) (s), 21.7 (d, J PC ) 6.0 Hz) (q),
17.6 (d, J PC ) 4.0 Hz) (q), 8.8 (t); (major isomer) 167.9 (d, J PC
) 9.0 Hz) (s), 150.1 (d, J PC ) 6.0 Hz) (s), 132.4 (d, J PC ) 7.0
Hz) (s), 131.6 (d, J PC ) 105.0 Hz) (s), 131-127 (d), 99.9 (d, J PC
) 107.0 Hz) (s), 21.1 (d, J PC ) 6.6 Hz) (q), 18.1 (d, J PC ) 6.6
Hz) (d), 17.3 (d, J PC ) 3.9 Hz) (q), 8.9 (t). Anal. Calcd for
C21H21OP: C, 78.73; H, 6.61. Found: C, 78.79; H, 6.68.
1,1-Dicyclop r op yl-4-(d ip h en ylp h osp h in yl)-2,3,4-p en -
t a t r ien e (10b). Reaction of 4d R and n-BuLi following the
general procedure gave 10b: 40% yield; IR 2060, 1440, 1180
J PC ) 100.4 Hz) (s), 96.0 (d, J PC ) 105.7 Hz) (s), 92.7 (d, J PC
)
14.8 Hz) (s), 39.6 (d, J PC ) 19.3, d, J PC ) 5.6 Hz) (s), 34.8 (s),
34.7 (s), 31.0 (q), 26.9 (d, J PC ) 5.8, d, J PC ) 2.9 Hz) (s), 23.7
(q), 23.0 (q), 22.0 (q), 20.3 (q), 18.5 (d, J PC ) 12 Hz) (q), 15.7
(d, J PC ) 7.8 Hz) (q).
X-r a y Cr ysta llogr a p h y of C54H70P 2O2 (14δ).53 C54H70
-
O2P2: Mr ) 813.11, triclinic, P1h, a ) 11.934(6) Å, b ) 12.521(3)
Å, c ) 20.560(5) Å, R ) 82.13(2)°, â ) 78.23(3)°, γ ) 71.11(3)°,
V ) 2837(2) Å-3, Z ) 2, Dx ) 0.952 mg‚m-3, λ(Mo KR) )
0.709 26 Å, µ ) 1.05 cm-1, F(000) ) 880, T ) 294 K, final R )
0.074 for 3919 observations. The sample (0.25 × 0.25 × 0.40
mm) is studied on an automatic diffractometer (Enraf-Nonis
CAD-4) with graphite monochromatized Mo KR radiation. The
cell parameters are obtained by fitting a set of 25 high-θ
reflections. The data collection (2θmax ) 50°, scan ω/2θ ) 1,
tmax ) 60 s, range hkl: h 0.14, k -14.14, l -24.24, intensity
controls without appreciable decay (0.3%) gives 9443 reflec-
tions from which 3919 independent (Rint ) 0.011) with I >
5σ(I). After Lorenz and polarization corrections the structure
was solved with direct methods which reveal many non-
hydrogen atoms of the molecule. The remaining ones, in
particular the disordered carbon atoms of the tert-butyl groups,
are found after successive scale factor calculations and Fourier
difference. After isotropic (R ) 0.11), then anisotropic refine-
ment (R ) 0.098), many hydrogen atoms may be found with a
Fourier difference. The whole structure was refined by the
full-matrix least-squares techniques (use of F magnitude; x,
y, z, âij for P, C, and O atoms, x, y, z, Biso for tert-butyl C atoms,
1
cm-1; H NMR (CDCl3) δ 7.7 (m, 4H), 7.4 (m, 6H), 2.2 (d, J )
9.8 Hz, 3H), 1.6-1.1 (m, 4H), 0.83 (m, 2H), 0.5 (m, 4H); 13C
NMR (CDCl3) δ 167.4 (d, J PC ) 9.0 Hz) (s), 144.0 (d, J PC
)
13.0 Hz) (s), 141.8 (d, J PC ) 8.0 Hz) (s), 131.2 (d), 127.9 (d),
127.8 (d), 127.7 (d), 97.7 (d, J PC ) 107.0 Hz) (s), 17.9 (d, J PC
)
8.5 Hz) (q), 16.5 (d, J PC ) 13.8 Hz) (d), 16.4 (d, J PC ) 13.7 Hz)
(d), 9.4 (t), 9.3 (t); 31P NMR (CDCl3) δ 28.7. Anal. Calcd for
C23H23OP: C, 79.75; H, 6.69. Found: C, 79.68; H, 6.76.
(3S*)-(E)-2-[1-(Diph en ylph osph in yl)eth yliden e]-5-[(S*)-
2-(d ip h en ylp h osp h in yl)p r op -1-en ylid en e]-1,1,4,4-t et r a -
m eth ylsp ir o[2.2]p en ta n e (14r). Reaction of 4bR and n-Bu-
Li following the general procedure gave 14R: 52% yield; mp
1
78 °C; IR 3050, 1990, 1440 cm-1; H NMR (CDCl3) δ 7.8-7.2
(m, 20H), 1.97 (d, J ) 11.6 Hz, 3H), 1.36 (d, J ) 12.2 Hz, 3H),
1.34 (s, 3H), 1.0 (s, 3H), 0.83 (s, 3H), 0.81 (s, 3H); 13C NMR
(CDCl3) δ 188.2 (d, J PC ) 9.0 Hz) (s), 151.7 (d, J PC ) 11.0 Hz)
(s), 131.5 (d), 128.2 (d), 116.5 (d, J PC ) 99.0 Hz) (s), 95.4 (d,
J PC ) 106.0 Hz) (s), 93.0 (d, J PC ) 14.0 Hz) (s), 40.1 (d, J PC
)
20.0 Hz, d, J PC ) 5.3 Hz) (s), 35.03 (d, J PC ) 3.7 Hz) (s), 27.0
(t, J PC ) 2.8 Hz) (s), 23.5 (q), 22.9 (q), 22.1 (q), 20.3 (q), 18.2
(d, J PC ) 12.6 Hz) (q), 15.5 (d, J PC ) 7.5 Hz) (q); 31P NMR
(CDCl3) δ 30.46 and 27.80; MS m/z 588 (2), 573 (2), 467 (2),
388 (7), 387 (44), 386 (29), 371 (27), 202 (47), 201 (100), 185
(55), 184 (77), 170 (18), 169 (16), 155 (15); HMRS calcd for
C38H38O2P2 588.23469, found 588.2339.
and x, y, z fixed for
H atoms; 506 variables and 3919
observations; ω ) 1/σ(Fo)2 ) [σ2(I) + (0.04Fo2)2]-1/2 with the
resulting R ) 0.076, Rw ) 0.074 and Sw ) 1.82 (residual ∆F
e 0.42 e Å-3).54 Atomic scattering factors were taken from
International Tables for X-ray Crystallography (1974). All the
calculations were performed on a Digital MicroVAX 3100
computer with the MOLEN package.55
(3S*)-(E)-2-[1-[Bis(4-ch lor op h en yl)p h osp h in yl]eth yli-
d en e]-5-[(S*)-2-[bis(4-ch lor op h en yl)p h osp h in yl]p r op -1-
en yliden e]-1,1,4,4-tetr am eth ylspir o[2.2]pen tan e (14â). Re-
action of 4bâ and n-BuLi following the general procedure gave
1
14â: 68% yield; IR 1995 cm-1; H NMR (CDCl3) δ 7.63-7.19
(m, 16H), 1.95 (d, J ) 11.9 Hz), 1.378 (d, J ) 12.4 Hz, 3H),
1.374 (s, 3H), 1.09 (s, 3H), 0.92 (s, 3H), 0.917 (s, 3H); 13C NMR
(CDCl3) δ 188.6 (d, J PC ) 9.0 Hz) (s), 153.3 (d, J PC ) 11.0 Hz)
(s), 138.9 (s), 133.2 (d, J PC ) 11.0 Hz) (d), 129.3-128.8 (d),
115.9 (d, J PC ) 101.0 Hz) (s), 95.3 (d, J PC ) 108.0 Hz) (s), 93.46
(d, J PC ) 13.0 Hz) (s), 40.6 (d, J PC ) 18.9 Hz, d, J PC ) 5.1 Hz)
(s), 35.8 (d, J PC ) 3.7 Hz) (s), 27.6 (s), 23.9 (q), 23.1 (q), 22.4
(q). Anal. Calcd for C38H34Cl4O2P2: C, 62.83; H, 4.72.
Found: C, 62.87; H, 4.81.
(3S*)-(E)-2-[1-[Bis(4-br om op h en yl)p h osp h in yl]eth yli-
d en e]-5-[(S*)-2-[bis(4-br om op h en yl)p h osp h in yl]p r op -1-
en yliden e]-1,1,4,4-tetr am eth ylspir o[2.2]pen tan e (14γ). Re-
action of 4bγ and n-BuLi following the general procedure gave
14γ: 41% yield; mp 133-134 °C; IR 1995, 1580, 1480, 1205
cm-1; 1H NMR (CDCl3) δ 7.41-7.32 (m, 16H), 1.78 (d, J ) 11.8
Hz, 3H); 13C NMR (CDCl3) δ 188.1 (d, J PC ) 9.0 Hz) (s), 152.8
(d, J PC ) 12.7 Hz) (s), 133-131 (d), 114.7 (d, J PC ) 100.0 Hz)
(s), 94.9 (d, J PC ) 107.0 Hz) (s), 93.0 (d, J PC ) 15.0 Hz) (s),
40.2 (d, J PC ) 19.3 Hz, d, J PC ) 5.4 Hz) (s), 35.3 (d, J PC ) 3.8
Hz) (s), 27.1 (d, J PC ) 6.2 Hz, d, J PC ) 3.0 Hz) (s), 23.8 (q),
23.0 (q), 22.3 (q), 20.6 (q), 18.1 (d, J PC ) 12.9 Hz), 15.2 (d, J PC
) 8.1 Hz). Anal. Calcd for C38H34Br4O2P2: C, 50.47; H, 3.79.
Found: C, 50.59; H, 3.74.
Ack n ow led gm en t. We thank Dr. I. D. R. Stevens
(University of Southampton, U.K.) for critical reading
of the manuscript. We are indebted to Dr. R. Faure for
his assistance in NMR measurements.
Su p p or tin g In for m a tion Ava ila ble: Tables of selected
bond lengths and angles for 14δ (1 page). This material is
contained in libraries on microfiche, immediately follows this
article in the microfilm version of the journal, and can be
ordered from the ACS; see any current masthead page for
ordering information.
J O970771U
(53) The authors have deposited atomic coordinates for this struc-
ture with the Cambridge Crystallographic Data Centre. The coordi-
nates can be obtained, on request, from the Director, Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ,
U.K.
(54) International Tables for X-ray Crystallography; The Kynoch
Press: Birmingham, 1974; present distributor, D. Reidel: Dordrecht.
(55) Fair, C. K. MolEN. An Interactive Intelligent System for Crystal
Structure Analysis; Enraf-Nonius: Delft, The Netherlands, 1990.