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Diastereoselective Reaction of a 1-Phosphaallyl Anion with an Alkyne Structure of an Isolated Dihydrophospholyl Anion and Stereospecific Protonation to Give 2 3-Dihydrophosphole.

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solution and a mixture of 5 o r 6 and protonated pyridine precipitated. The latter was
removed by fractional recrystallization from CH,CI,!Et,O.
Synthesis of 5 and 6 from 2: A solution of 2.5 mmol of 2 in 20 mL of CH,CI, was
treated with 2 5 inmol of Me,SiOTf. Then 6 mmol of diazo ester 3 o r 4 was added
dropui\e. which was accompanied by release of N,.30 min after N, release had
stopped. Et,O \bas added and 5 or 6 precipitated. Both compounds were removed
by liltrntion. washed, and dried at 0.01 Torr.
Synthesis o f 7 12:A solution of 2 mmol of 6 in 20 m L of CH,CI, was treated with
2.5 mmol oi'the appropriate nucleophile. Alier 1 h the corresponding products were
precipitated by addition of EtzO. removed by filtration, washed with Et,O. and
dried i l l 0 01 Torr.
~
Table 1 Yields and spectroscopic data of compounds 5 1 2 [a]. Correct C,H.N
analyses were d s o obtained.
5 Yellow powder: yield: 8 4 % [b]; ' H NMR (CD,CN): 6 = 1.46 (s. 9 H ; CH,). 7.58
(t. 2 H . H-3:H-5 Ph). 7.75 (t. 1 H ; H-4 Ph), 8.10 id. 2 H ; H-2!H-6 Ph): ' T N M R
(CD,CN) [c]: 6 = 28.14 (CH,). 87.00 (C(CH,),). 117.63 (C-l Ph), 121.70 (9.
' J ( C . F ) = 320 HL; CF,), 133.05 (C-3;C-5 Ph), 134.25 (C-4 Ph). 136.24 (C-2;C-6
Ph). 161) 86 (COI: I R : 3[cm-'] = 2100 (N,). 1700 (CO).
6 Yellowpowder,?.ield: 8 1 % [b]; ' H N M R ( C D , C N ) : 6 =1.25(1.3H;CH,).4.28
(q. 2 H , CH2).7.5X (t. 2 H : H-3/H-5 Ph). 7.74(t, 1 H: H-4 Ph). 8.13 (d. 2 H ; H-2iH-6
Ph); "C'NMR (CD,CN) [c]: S ~ 1 4 . 4 9(CH,). 65.14 (CH,). 117.71 (C-l Ph).
121.65 (q. ' J ( C . F ) = 320 Hz; CF,), 133.04 (C-3:C-5 Ph). 134.33 (C-4 Ph), 136.47
(C-?:C-6 Ph). 162.12 ( C O ) :IR: G[cin-'] = 2100 (N2). 1710 (CO).
7: Yellou,powder:yield:74%; ' H N M R ( C D , C N ) : d =1.30(t.3H;CH,),4.35(q.
Z H , C H , ) . X.20(t,2H:H-3/H-5pyridine).8.72(t,lH; H-4pyridine). 8.90(d,ZH;
H-2:H-6 pyridine): " C N M R (CD,CN) [cl: 6 =14.57 (CH,). 64.13 (CH,), 122.00
(q, ' J ( C . F ) = 320 Hr: CF,). 130.00 (C-3.C-5 pyridine). 149.54 (C-4 pyridine).
150.25 i C ' - 2 C 6 pyridine), 161.35 (CO). i.[cm-'] = 2115 (Nz). 1710 (CO).
8~Colorle.;apowder:yield:90%:'HNMR(CDCI,):fi=1.35(1. 3H;OCH2CH,).
3.33 (5. 6 H : S(CH,),). 4.35 (q, 2 H ; OCH2CH,); ',CNMR (CDCI,): 6 =14.08
(0CH:C.H %). 27.53 (S(CH,),). 55.10 (CNI). 63.40 (OCH,CH,). 120.46 (4,
'J(C7.F) = 320 Hz: CF,), 160.29 ( C O ) . IR. ?[cm-'] = 2140 (N2). 1695 (CO).
9: Light?cllowpowder;yield: 9 5 % : ' H N M R ( C D C I , ) : 6 =1.20(t.3H:CH3).4.27
( q . 4 H : C H J . 7.78lmc, 15H;AsPhJ: "CNMR (CDCI,)-fi =13.99(CH3), 50.71
(CN,). 63.65 ( C H 2 ) . 119.74 (C-l AsPh,), 121.00 (9, ' J ( C . F ) = 320 Hz; CF,).
131.38 (C'-3.C-5 AsPh,), 132.80(C-2;C-6 AsPh,), 135.14(C-4AsPh3). 162.66(CO);
1 R : 3[ctn-'] = 3140 (N,). 1705 (CO).
10: Light yellow powder. yield: 86%: ' H N M R (CDCI,): 6 =1.27 (t, 3 H ; CH,),
4.01 (4. 4 H : CH,). 7.64 (mc. 1 5 H ; SbPh,); '"CNMR (CDCI,): 6 ~ 1 3 . 8 1(CH,),
4X.16(CN2).62.25 (CH,). 121.00(q. 'J(C,F) = 320 Hz;CF,). 127.62(C-l SbPh,),
130.6O(C-3'C-5SbPh,). 133.04(C-4 SbPh,). 134.44 (C-2X-6SbPh3). 166.13 (CO);
IR: < [ c m - ' ] = 7110 (N?). I680 (CO).
11: Light yellow powder: yield: 53%: ' H N M R (CDCI,): 6=1.33 (t. 3 H :
O C H 2 C I I , ) .1 42 (t. 9 H ; N(CH,CH,),). 3.85 (4, 6 H ; N(CH,CH,),). 4.35 (4, 2 H :
OCH,CH,): I 3 C N M R (CDCI,): 6 = 8.49 (N(CH,CH,),). 14.40 (OCH,CH,),
56.42 (NIC'H,CH,),). 63.54 (OCH,CH,). 79.02 (CN,). 121.11 (4. ' J ( C , F )=
370 Hr. Cb,). 160.11) (CO): I R : G[cm-'] = 2110 (N,), 1700 (CO).
12:Colorlesspowder;yield:72%:'HNMR(CD,CN):6= 0.91(t. 3H;CH,). 3.96
(q. 2 H : CHJ. 7.42 (mc, 30H: PPh,): I 3 C N M R (CD,CN) [c]: 6 =14.16 (CH,),
62.04 (CHI). 321.44 (d, 'J(C.P) = 88.2 Hz. C-l PPh,). 122.00 (q, 'J(C.F) =
320 Hz. CFO. 124.23 (d. 'J(C,P) = 95.6 Hz: C-1 PPh,). 130.36 (d, 3J(C,P) =
12.9 HZ: C-3.C-5 PPhJ. 130.56 (d, ,J(C,P) ~ 1 2 . Hz;
9 C-3.C-5 PPh,), 134.16 (d,
*J(C.P) = 9.7 Hz; C-2!C-6 PPh,), 134.42 (d, 'J(C,P) =11.0Hz: C-2/C-6 PPb,).
134.69 ( d . 'J(C.P) = 2.9 Hz; C-4 PPh,). 135.03 (d. 4J(C.P) = 3.7Hz; C-4 PPh,),
164.12 id. ' J ( C . P ) = 29.4Hz; C O ) . " P N M R (CD,CN): 6 = 6.49 (PPh:). 27.17
(N = P P h , ) .
[a] ' H N M R (400MHr. 25 C. TMS), I3CNMR (100MHz. 25°C. TMS). "P
NMR (100 MHr. 25 'C. H,P04), IR spectra measured in nujol. [b] Yield based on
the ~ynthe\isfrom 2. [c] The signal of the quaternary diazo carbon atoin was not
evident in any of these "C N M R spectra.
Received: May 25. 1994 [Z6967IE]
German version: A n g e w CIimi. 1994. /06.2038
[ I ] T. Curtius, Brr. Disc/?. Cltivn. Ges. 1883. 16, 2230-2231.
[2] Reviews. a) M. Regitz, G. Maas, Diuro Compoimds. 1st ed Academic Press,
Orlando. 1986: b) M. Bohshar. J. Fink, H. Heydt. 0 . Wagner. M . Regitz,
Mefhodiw 0 r ' ~ Chiwi.
.
(Hinibm- Wi,xl) 4rh i d /YS?-, Vol. E14h. 1990. p. 961
1371.
[1] Reviews' a ) C . Willgerodt. Die Orgunischeii Verbiiidungen a.irli Mehrirrrttgmni
lud, Enke. Stuttgart. 1914; b) R. M. Moriarty. 0. Prakash. Acc. Chrm. Rex
1986, JY. 244-250: c) A. Varvoglis. S,wrhesr.\ 1984, 709-726; d ) G. F. Koser in
llir Chcniisrri. of Funi,/ionul Groupv. Supp/~n?iwfD (Eds.: S. Patai. 2 . Rappoport). Wiley. Chrchester. 1983. pp. 1265-1351 : e) A. Varvoglis. Climz. Sot.
.
Rrr. 1982. f0. 377 -407; f) R. M. Moriarty, R. K. Vaid. L~vnrhr.si.r1990. 431
447; g) D. F. Banks, Chem. Res. 1966, 66.243- 266; h) R. M Moriarty, R . K .
Vaid, G. F. Koser. Synletr 1990. 365 -383: i) P J. Stang. A n g r w . Chein. 1992.
104.281 -292; Angew. Chem. Inr. Ed. Engl. 1992.31,274-285: j) A. Varvoglis,
The Orgrinic Chemisfrj uf Polvcoordnuterl l o i i i n ~ ,1st ed.. VCH. Weinheim,
1992.
(41 R. Weiss. J. Seubert, Angeu.. Chiwi. 1994. 106. 900-901; Angeiv. Chetn. In!. Ed.
E q I . 1994, 33, 891 -893.
(51 When 4 was allowed to react for more than 1 h, 7. the product of nuclcophilic
substitution. was obtained directly. Under analogous conditions 5 did not
react.
[6] By striictural variation of the diazo compound this alternative synthetic route
provided a broad spectrum of these compounds.
[7] The initial step is most likely silylatton of the diazo compound, during which
one equivalent of the diazo compound is consumed as an auxiliary base. Cf.:
M. Martin, S w r h . Connnun. 1983,13,809-811: H. Emde. G Simchen, Liehif$s
Ann. Chem. 1983. 816-834; c) T. Allspach. H. Gumpel. M. Regttz, J.
Orgunnmrr. Cheni. 1985. 290. 33 -39.
[8] Crystal structure analysis of 5 (C,,H,,F,IN,O,S); M = 494.22. monoclinic.
space group P2(1)/c, u = 15.066(3), b = 10.769(2), c = 12.500(2) A, Y = 90,
/1=113.75(3).;'= 9 0 . V = 1 8 5 6 . 3 ( 6 ) A " Z 2 = 4 , p ~ ~ , ~ , = 1 . 7Mgm-3,
68
12224
reflections (4.0 > 2 0 54.0-). of which 4098 were independent. R1 = 0.0495
for 2945 reflections with I.'.4u(F); wR2 = 0.1465 for all data (wR2 s [Xw(F:
F~)z:[Z~i(F~]1~2);
the measurement was conducted with an automatic fourcircle diffractometer Nicolet R3miV with Mo,, radiation .(; = 0.71073) at
200K. The structure was solved by direct methods (SHEXTL Plus 4.11
(Siemens)). All non-hydrogen atoms were refined anisotropicically versus F';
the hydrogen atoms were retined isotropically in idealized. fixed positions
according to a riding model (SHELXL93, G. M. Sheidrick. Universitit
Giittingen. 1993). Further details of the crystal structure investigation may be
obtained from the Fachinformationszentrum Karlsruhe. D-76344 EggensteinLeopoldshafen (FRG) on quoting the depository number CSD-58387.
[9] This value indicates that the coordination of the anion is weaker here than that
in an iodonioacetyleiie described by Stang et 31: P. J. Stang. A . M. Arrf. C . M.
Crittell. Angew. Chem. 1990. /I)?,307-308; Angeir. Chon. lnr. Ed. EngI. 1990,
ZY. 287.
[lo] S. Sorriso in The Chiwiisfrj of die Dfuzoriiiini and Diazo Group. Vol. 1 (Ed.: S.
Patai), Wiley, Chichester. 1978. pp. 95- 135.
[l I ] A Varvoglis. The, Organic Chemirtr,v 01 Pol~coordinufedlo~ltni~.,
1st ed.. VCH.
Weinheim, 1992. p. 209-211, 315-317, and references therein.
[12] M. Regiti. A. E. M. Tawfik, H. Heydt. Liebigs Ann. Chrm. 1981. 1865 1873.
~
~
Diastereoselective Reaction of a 1-Phosphaallyl
Anion with an Alkyne: Structure of an Isolated
Dihydrophospholyl Anion and Stereospecific
Protonation to Give 2,3-Dihydrophosphole**
Edgar Niecke," M a r t i n Nieger, and Peter Wenderoth
Dedicated to Profkssor Reinhard Schmutzler
on the occasion of his 60th birthdaj)
Polar cycloaddition reactions are well documented for 2-azaand 1.2-diazaallyl "anions" and have proved to be successful for
the construction of heterocycles.['] This reaction sequence is
used particularly for the synthesis of 3,4-dihydro-2H-pyrroles.
pyrrolidines, and pyridene derivatives.[21 In contrast, corresponding cycloaddition reactions of ally1 anions are rare and are
limited to compounds whose substituents are capable of stabilizing the negative charge in the 2-position.['. 31
In the context of work on phosphaallyl anions'41 we recently
reported on a surprisingly simple synthesis of the phosphindolyl
system.15]We have now extended our investigations on l-phos-
-
Ait,ccw Clwm I n f . Ed EngI. 1994. 33. N o . IY
[*I
[**I
Prof. Dr. E. Niecke, Dr. M. Nieger. DipLChem. P. Wenderoth
Anorganisch-Chemisches Institut der Universitit
Gerhard-Domagk-Strasse 1. D-53121 Bonn (FRG)
Telefax: Int. code + (228)73-5327
This work was supported by the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie.
": VCH Vcrlugsgi~.r~~l/.rchu/r
mbH, 0.69451
Weinbrim, 1994
057U-OR33/Y4;fYlY-I953$ 10.00+ .25:0
1953
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phaallyl systems to cycloaddition reactions and have successfully synthesized and structurally characterized a heterocyclic system with a noncomplexed allyl anion as the central building
block. The existence of separate ion pairs for allyl anionic systems has to our knowledge only been demonstrated by NMR
spectroscopic investigations.[61
The equimolar reaction of the I-phosphaallyl anion 1 with
tolane, which is accompanied by a change in color from purple
to deep red, leads to the formation of an anion 2. This can be
isolated as 2. Li(dme), in the form of extremely air-sensitive
crystaIs.”]
Ph
The lithium salt of the dihydrophospholide 2 crystallizes i n
the chiral space group P2,2,2, .Ia1The lithium ion resides in an
octahedral environment coordinated by three solvent molecules
(DME) . The shortest distances to the anion lie in the range of
van der Waals contacts and thus confirm the presence of separate ions in the crystal. The anion has the absolute configuration
P I : S , C4: S in the single crystal chosen for the structure analysis. The five-membered ring has a slightly twisted envelope conformation with the phosphorus atom at the vertex (Fig. 1 ) .
Three of the five phenyl substituents (on C 1-C3) are arranged
propellerlike about the framework of the ring. The phenyl
group at the phosphorus atom adopts a “flag pole” position and
is orientated trans with respect to the substituent on C4. The
allylic structure C 1-C 3 results from the short distances (C 1
C2 141.2(8); C 2 - C 3 139.5(8) pm). which, like the innercyclic
angle at C 2 (117.0(5)“), lie in the range of values typical for
allyllithium complexes.[’ ‘I The bonds from these atoms to the
ips0 carbon atoms of the phenyl groups (C 5. C 11, and C 17)
correspond to single bond lengths (146 148 pm) between sp2hybridized carbon centers. As expected the distances of C 4 to
C 3 and to C23 (154-155 pm) are longer. The bond lengths
P I - C 4 and PIGC29 (187.1(6) and 184.7(6)pm. respectively)
correspond with the expected values for this combination of
elements, in contrast, the P I -C 1 bond is significantly shorter
than expected (177.4(6) pm) . This indicates a stabilization of the
negative charge with the participation of the phosphorus
atom.[”]
No evidence for the formation of an intermediate is obtained
by following the reaction 1 + 2 by 31P NMR spectroscopy in
the temperature range - 60 < T < 25 “C. The exclusive formation of one product (31PNMR: 6 = 36.8) indicates a reaction
path,[’31in which following the cycloaddition the anion 3 containing a localized double bond is stabilized by a suprafaciul
[I ,3]-H shift to give the allylic system 2. Investigations on the
mechanism of the cycloaddition of allyl anions to (E)-stilbene[’3bbllead to the belief that also for 1 the thermodynamically
more unfavorable ( Z , Z )isomer[411a takes part in the reaction.
-
-
L!
C14
,
o
$
Php
Ph
c29
4
- 1,3-H
Php-
C(Ph)-C(PhFC(Ph)
-C(Ph)H
1-
5
0
c23
Fig. 1. Crystal structure of the anlon of L.Li(dme), . Selected bond lengths [pm] and
angles [ I . PI-Cl 177.4(6). PI-C29 184.7(6). PLC4 187.1(6), C1-C2 141.2(8). C2-C3
139.5(8), C3-C4 154.2(8); Cl-Pl-C29 102.0(3). Cl-Pl-C4 92.0(3). C4-Pl-CZ9
99.2(3), C2-CI-CS 130.5(6). C2-Cl-PI 110.4(5), CS-C1-PI l19.0(5). C3-C2-C1
117.0(5). C3-CZ-CI 1 120.5(6). Cl-C2-C11 122.4(6), CZ-C3-C17 130.2(6). C2-C3C4 111.9(6). C17-C3-C4 117.X(S).
1954
0 VCH Ci,rlu~.~~~,.~Pllslhajf
m h H , D-69451 Weirihebn, 1994
6
S 10.00+ .ZjO
0570-0833,’94~1919-1954
A n g i w Chem. Int. Ed. Engl. 1994, 33, N o . 19
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For a multistep reaction[141it must be assumed that the acyclic
"anion" 4 generated in the first step of the reaction rapidly
cyclizes and thereby prevents the formation of a 1 -phosphapentadienyl anion 5.[151
Regardless of the course of the reaction by path (a) or (b) the
formation of only one product implies the highly stereoselective
course of the reaction, and the occurrence of pairs of enantiomers is to be expected. The presence of a racemic mixture is
supported by the protonation of 2 to give the corresponding
2,3-dihydrophosphole 6 , [ I 6 l which occurs strictly regio- and
stereospecifically with the formation of one product, in which
both enantiomers are present in the equal amounts.["I
The composition and constitution of 6 can be derived from
the high resolution mass spectrum (molecular peak) and the
results of multinuclear NMR measurements. The double bond
in the 4-position is confirmed by the two resonances in the
olefinic region (6 =142.2. L P= 8.8 Hz, and 147.4, 13.7 Hz),
whose chemical shifts, like the size of the couplings to the phosphorus nucleus. correspond to known values for 2,3-dihydrophospholes." 81 The geometry of the two ring hydrogen
atoms cannot be derived unambiguously from the 'H NMR
data (ii= 4.9, JH,p
= 6.9 Hz, and 4.5, 8.3 Hz; JH,H
= 8.3 Hz),
however, in a kinetically controlled reaction the protonation
should lead to a cis arrangement of the hydrogen atoms.
Investigations into the dipolar cycloaddition of 1-phosphaally1 anions with heteropolar multiple bonding systems are currently in progress.
[l I] G. Boche, H. Erzrodt, M. Marsch, W. Massa. G. Baum. H. Dietrich, W. Mahdi.
Angew. Chem. 1986,98,84-85;Angew. Chem. Inr. Ed. EngI. 1986.175.104-105:
see likewise: T. Clark, E. Jemmis, P. von R. Schleyer, S. Binkley. J. Pople, J
Organumet. Chem. 1978, 150, 1-6.
[12] The lithium salt of a phosphinomethanide, Me,PC(H)SiMe,. Li(pmdta) also
shows a comparably short P-C distance of 177.6 pm: H. K. Karsch, K . Zellner, P. Mikulcik. J. Lachmann, G. Miiller, Orgunometullrc.\ 1990. 9, 190-194.
[I31 See also: a) T. Kauffmann. K. Habersaat, E. Koppelmann. Angru. Chrm.
1972, 84. 262-263: A n g w . Chem. l n t . Ed. Engl. 1972. I t . 291-292: b) W, T.
Ford, G. F. Luteri, J Am. Chem. Suc. 1977, 99, 5330-5333.
[14] W. Bannwarth, R. Eidenschink, T. Kauffmann, Angrit'. Chwn. 1974, 86. 476477; Angew. Chem. I n f . Ed. EngI. 1974. 13, 468-469.
[15] Such a reaction course is observed for the reaction of the silylated 1.2-diphosphaallyl anion [Me,SiPPC(SiMe,)J
with a phosphaalkyne: G. Becker, personal communication.
1161 6: A solution of 2 (1.6mmol) in DME ( 5 mL) was allowed to react with an
equimolar amount phenylacetylene at room temperature. On stirring 6 began
to precipitate after 5 h. To complete the reaction the mixture was left o%ernight
and the white product was subsequently filtered through a frit. Repeated washing with DME and subsequent drying under high vacuum afforded 6 (619 mg,
83%). 3 1 PN M R (C,D,. external H,PO,): 6 = 27.3 (pseudo-q, J ( P , H ) =
7.6 Hz). "CI'H) and I3Cj1H, "P) N M R (CDCI,, external TMS. ring and
ipsu C atoms): 6 =147.4 (d. J(P,C) =13.7 Hz), 142.2 (d,J(P,C) = 8.8 Hz),
138.9, 138.7 (d, J(P,C) = 14.5 Hz). 138.2 (d, J(P,C) = 0.9 Hz). 137 9 (d,
J(P,C) = 24.4 Hz), 137.X(d,J(P,C) =13.8 Hz),64.2(d.J(P.C) = 5.0 H7..CH).
58.3(d,J(P.C) =7.2 Hz.CH). 'HNMR(CDCI,,internalTMS: ringprotons):
6 = 4.9 (dd, J(P.H) = 6.9 Hz, J(H H) = 8.3 Hz). 4.5 (dd. J(P.H) = X.3 Hz,
J ( H , H ) = 8.3 H7); MS (characteristic fragments): 466 ( 7 0 % ) [2.I 'I. 389 ( 8 % )
[Mi-Ph]. 288 (12%) [M+-Ph,C,]. 178 (94%) [Ph,C:]. 91 ( 5 9 % ) [C,HI I.
77 (80%) [Ph'], 51 (57%) [C4Hi].
[I71 The enantiomeric ratio of 6 was determined to be 1 : l in (+)-(R)-1-phenylethylamine as solvent ("P N M R : 6 = 25.8, 25.9). Rotation: 2 =1.5(10)'.
[18] L. D. Quin. S. G. Borleske, R. C . Stocks, Org. Muyn. Reson. 1973.5. 161-162.
Received: April 30, 1994
Revised version: June 15, 1994 [Z6885IE]
German version: Aizgew. Chem. 1994. 106. 2045
R. R Schmidt. Angeic. Chmi. 1973. 85. 235-270; Angrw. Chrm. I n t . Ed. EngI.
1973, I.?. 212-247; T. Kauffmann, ihid. 1974. 86, 715 -750 and 1974. 13,
627 662.
A . Dehnel. J. M. Kanabus-Kaminska, G. Lavielle. Can. J Chem. 1988, 66,
310- 318. T. Konakahara. N . Sugania. K . Sato, H r r e r o c w l r s 1992. 33, 157160.
G. Boche. P. Martens, Angew. Chcvn. 1972. X4, 768-769: Angeic. Chum. l n ~ .
Ed. En,yI. 1972. I t . 724-725.
E. Niecke, M. Nieger. P. Wenderoth. J. Am. C h m . SOC.1993, 115.6989-6990.
E. Kiecke. M. Nieger, P. Wenderoth. Angeu. Chem. 1994. 106, 362-363;
Angoii~.Chcw 1111. Ed. Engl. 1994. 33, 353-354.
D. H O'Brien, C . R. Russel, A. J. Hart. J. Am. Chem. SOC.1976, YH, 7427-7429.
Structures of ally1 anions as contact ion pairs are known: H. Bock, K. Ruppert,
2. Havlas. D. Fenske, Angew. Chem. 1990. 102. 1095-1097; Angew. Chrm. Itit.
Ed Eiigl. 1990,179. 1042.1044; G. Boche. G . Fraenkel. J. Gabral, K. Harms. N.
J. R . van Eikema Hommes, J. Lohrenz, M. Marsch, P. von R. Schleyer. J Am.
Chiwi. Soc. 1992. 114. 1562-1565.
2,Li(dnic),: The lithium salt of 1 (1.6 mmol) in D M E ( 5 mL) was allowed to
rract at room temperature with tolan (1.6 mmol). dissolved in D M E (7 mL),
and stirred for 2 h at 25 C. Crystallization at 4 ' C afforded 2.Li(dme), as red
orthorhombic crystals in 5 3 % yleld. "P N M R (DME. external H,PO,):
6 = 36.X. "C{'H} N M R (DME. external TMS: ring and i p o C atoms): 6 =
153.1 (d. J ( P C ) - l l X H r ) . 153.0 (d. J(P.C)=Y.O). 150.0 (d, J(P,C)=
12.1 1 3 ~ ) .146.7 (d. J(P.C) = 4.2 Hz), 144.3, 144.1 (d, J(P,C) =17.6Hz), 71.2
Id. J(P.C) = 3.0 H L . CH). 68.4 (d, J(P.C) = 14.9 Hz). The doublet structure of
an additional resonance (d ca. 61) is obscured by one of the DME signals.
red
X-ray structure analysis of 2.Li(dme), ([C,,H,,P]-[Li(C,H,,O,),li):
cryatals. crystal dimensions 0.20 x 0.25 x 0.40 1nm3:M = 742.8: orthorhombic,
space group. P 2 , 2 , 2 , (no. 19). u =11.587(1), h =16.981(4). c = 22.089(4) A.
V=4.346(1)nrn3. Z = 4 . ii(Cu,,)=0.91 min-', T = 2 0 8 K . F(000)=1592.
9604 i-eflections up to 2H,,, = 120 were measured on an Enraf-Nonius CAD4
diffractometer with the Cu,, radiation, 5985 of which were independent and
were uaed for all calculations. The structure was solved by direct methods and
refined to F' anisotropically. the H atoms were refined with a riding model
(program: SHELXL-93 [9]). The final quality coefficient w R 2 ( F Z )was 0.202,
with ii conventional R ( F / = 0.072 for 488 parameters and 255 restraints. An
extinction correction was carried out. The absolute structure was determined
by .\-refinement [lo]. Further details of the crystal structure investigation may
be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen ( F R G ) on quoting the depository number CSD-58316.
[9] G . M . Sheldrick. SHELXL-93. Universitit Gottingen, 1993.
[lo] H. D Flack. Acre C r y t u h g r . Sect. A 1983. 3Y, 876-881.
Anynv.
Uiim
ltn. E d W g I . 1994, 33, N o . 19
:{,
Cydopropanation by Methylene Transfer from
(qZ-Forma1dehyde)zirconoceneComplexes**
Gerhard Erker,* Stefanie Schmuck,
and Maximilian Bendix
Dedicaled to Professor Thomas Kauffmann
on the occasion of his 70th birthday
Multinuclear (q2-forma1dehyde)zirconocene complexes have
some properties that are reminiscent of the chemistry of methylene on metal oxide surfaces."] Thus, [{(q2-CH,0)ZrCp,},]
(1)12'reacts similarly to diaz~methane[~I
with catalytic amounts
of triethylborane to give a smooth CH, transfer and methylene
oligomerization. After oxidative workup of the resulting product
mixture of alkylborane compounds, a Poisson distribution of
I-alkanols HO(CH,),C,H, with a degree of oligomerization n
of up to 15 is obtained.r41A natural extension of this work was
to test whether the CH, groups of 1 could also be transferred to
simple alkenes with cleavage of the good zirconocene oxide
leaving group and thus produce cyclopropanes. Although with
complex 1 such a direct transformation was not possible, this
cyclopropane formation took place at a binuclear p-oxozirconocene complex that bears a Z r - 0 bridging CH, group and
a c-bound alkenyl ligand simultaneously at the metal oxide
matrix.
We have shown that 1 reacts with the metallocene chlorides
[Cp,MCI,] of zirconium and hafnium to yield the dinu[*] Prof. Dr. G. Erker, Dr. S. Schmuck, Dr. M. Bendix
Organisch-chemisches lnstitut der Universitit
Correnstrasse 40, D-48149 Miinster (FRG)
Telefax: Int. code (251)83-9772
+
[**I
This work wassupported by the Fonds der Chemischen Industrie. the Deutschc
Forschungsgemeinschaft. and the Alfried-Krupp-vou Bohlen-und -HalbachStiftung.
VCH Verlugsgr.cell.s~hufimbH, D-69451 Weinheim, 1994
0570-0833/Y4/1Y19-lY55Y 10.00+.25.;(1
1955
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diastereoselective, structure, stereospecific, reaction, dihydrophosphole, protonation, isolated, phosphaallyl, dihydrophospholyl, alkyne, give, anion
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