Carbon-oxygen reductive-elimination from nickel(II) oxametallacycles and factors that control formation of ether, aldehyde, alcohol, or ester products

Full text of DOI:10.1021/ja9714999

J. Am. Chem. Soc. 1997, 119, 8135-8136
8135
Carbon-Oxygen Reductive-Elimination from
Nickel(II) Oxametallacycles and Factors That
Control Formation of Ether, Aldehyde, Alcohol, or
Ester Products
o-C6H4) (1) with paraformaldehyde.6 Monomeric analogues of
2 containing bidentate ligands were prepared by stirring THF
or ether solutions of 2 with 1,2-bis(dimethylphosphino)ethane
(dmpe) or 2,2′-bipyridine (bpy), giving high yields of (dmpe)-
NiOCH2CH2CMe2-o-C6H4 (3)6 and (bpy)NiOCH2CH2CMe2-o-
Runyu Han and Gregory L. Hillhouse*
C6H4 (4), respectively.
Searle Chemistry Laboratory, Department of Chemistry
When benzene solutions of 2 are stirred under dry O2 (1 atm),
a slow reaction ensues over the course of 72 h at ambient
temperature resulting in formation of a new C-O bond via
oxidatively-induced reductive-elimination to give 4,4-dimeth-
The UniVersity of Chicago, Chicago, Illinois 60637
ReceiVed May 9, 1997
Reductive-elimination reactions from transition-metal com-
plexes comprise one of the most ubiquitous and synthetically
useful families of organometallic reactions.1 Recent research
aimed at extending reductive-elimination reactions from the
common classes that form new C-H and C-C bonds to include
those that form C-X bonds (where X ) O, S, N, halide, etc.)
has been intense.2,3 Of particular note are processes catalyzed
by Pd phosphine systems that afford arylamines via key C-N
reductive-elimination steps.4 Recently, this chemistry has been
elaborated to provide new synthetic routes to arylethers via C-O
elimination.5
ylchroman, o-C6H4CMe2CH2CH2O (5), in 39% isolated yield
(eq 2).7 Under these conditions the PMe3 ligands of 2 are
We are actively investigating reductive-elimination reactions
in nickel(II) systems that form new C-N and C-O bonds.3
Alkylnickel(II) amides {i.e., LnNi(R)(NR2)} were shown to react
with oxidants in a one-electron process to give high yields of
C,N-reductive-elimination products, especially when the alkyl
and amido moieties are tethered together in the form of an
azametallacycle (as shown in eq 1).3d In contrast, C-O
oxidized to OdPMe3, and an intractable black precipitate is
formed that contains the Ni. As for C-N elimination upon
oxidation of Ni(II) amido alkyl complexes, the role of O2 is
probably to carry out oxidation of Ni(II) to Ni(III) (eq 2),3d
a
transformation that can also be effected by use of the one-
electron oxidant (1,1′-diacetylferrocenium)silver tetrafluorobo-
rate, (AcC5H4)2Fe‚AgBF4.8 The monomeric oxametallacycles
3 and 4 react in a similar fashion with O2, giving 5 in ∼40%
isolated yields, although the reaction of 3 with O2 is significantly
faster than those of O2 with 2 or 4.
The reactivity of 2 with oxygen differs dramatically from its
thermal reactivity in the absence of an oxidant. Heating a
benzene solution of 2 at 100 °C for 12 h causes a color change
from canary yellow to dark yellow. Removal of the solvent
under vacuum and extraction of the residue with hexanes
followed by chromatographic workup allows for isolation of
3-methyl-3-phenylbutyraldehyde, PhCMe2CH2CHO (6), in 50%
eliminations from related Ni(II) complexes are not very efficient
and are limited to cyclic derivatives.3a,b Herein we report on
our studies of the (i) thermal and (ii) oxidatively-induced
reaction chemistries of the dimeric seven-membered nickel(II)
1
yield, with no formation of the chroman 5 (confirmed by H
NMR). Thus, thermolysis of 2 favors â-hydrogen elimination
from the seven-membered oxametallacycle followed by C-H
reductive-elimination to give 6 as shown in eq 3. While there
oxametallacycle [(PMe3)NiOCH2CH2CMe2-o-C6H4]2 and its
related monomeric Ni derivatives.
Dimeric [(PMe3)NiOCH2CH2CMe2-o-C6H4]2 (2) was syn-
thesized according to the method of Carmona by the room-
temperature reaction of THF solutions of (PMe3)2Ni(CH2CMe2-
(1) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles
and Applications of Organotransition Metal Chemistry; University Science
Books: Mill Valley, CA, 1987.
(2) (a) Hoberg, H.; Schaefer, D.; Burkhart, G.; Kruger, C.; Romao, M.
J. J. Organomet. Chem. 1984, 266, 203. (b) Villanueva, L. A.; Abboud, K.
A.; Boncella, J. M. Organometallics 1994, 13, 3921. (c) Baranano, D.;
Hartwig, J. F. J. Am. Chem. Soc. 1995, 117, 2937.
is little precedent for â-H elimination from oxametallacycles
to give aldehydes, analogous â-hydrogen elimination is a
common pathway for the decomposition of acyclic alkoxide
complexes.9 Heating solutions of the dmpe and bpy complexes
3 and 4 at 100 °C likewise gives aldehyde 6 in lower yields,
with varying relative rates for the eliminations and with
formation of two significant coproducts. As shown in eq 4,
thermolysis of 3 results in competitive formation of aldehyde 6
along with significant amounts of ester 7. The relative yields
(3) (a) Matsunaga; Hillhouse, G. L. J. Am. Chem. Soc. 1993, 115, 2075.
(b) Matsunaga, P. T.; Mavropoulos, J. C.; Hillhouse, G. L. Polyhedron 1995,
14, 175. (c) Koo, K.; Hillhouse, G. L.; Rheingold, A. L. Organometallics
1995, 14, 456. (d) Koo, K.; Hillhouse, G. L. Organometallics 1995, 14,
4421. (e) Koo, K.; Hillhouse, G. L. Organometallics 1996, 15, 2669.
(4) (a) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116,
7901. (b) Paul, F.; Patt, J.; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116,
5969. (c) Guram, A. S.; Rennels, R. A.; Buchwald, S. L. Angew. Chem.,
Int. Ed. Engl. 1995, 34, 1348. (d) Driver, M. S.; Hartwig, J. F. J. Am. Chem.
Soc. 1995, 117, 4708. (e) Louie, J.; Hartwig, J. F. Tetrahedron Lett. 1995,
36, 3609. (f) Wolfe, J. P.; Wagaw, S.; Buchwald, S. L. J. Am. Chem. Soc.
1996, 118, 7215. (g) Driver, M. S.; Hartwig, J. F. J. Am. Chem. Soc. 1996,
118, 7217.
(6) Carmona, E.; Gutierrez-Puebla, E.; Martin, J. M.; Monge, A.;
Paneque, M.; Poveda, M. L.; Ruiz, C. J. Am. Chem. Soc. 1989, 111, 2883.
(7) Experimental, spectral, and analytical details are given in the
Supporting Information.
(8) Carty, P.; Dove, M. F. A. J. Organomet. Chem. 1971, 28, 125.
(9) Brynza, H. E.; Tam, W. Chem. ReV. 1988, 88, 1163.
(5) (a) Palucki, M.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc.
1996, 118, 10333. (b) Mann, G.; Hartwig, J. F. J. Am. Chem. Soc. 1996,
118, 13109. (c) Palucki, M.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem.
Soc. 1997, 119, 3395.
S0002-7863(97)01499-6 CCC: $14.00 © 1997 American Chemical Society

8136 J. Am. Chem. Soc., Vol. 119, No. 34, 1997
Communications to the Editor
Scheme 1
Scheme 2
of 6 and 7 are dependent on the initial concentration of the
oxametallacycle 3, with the partition favoring 7 with increasing
initial [3].
M-H, M-C, and M-O bonds have been reported,11 and
sequential insertions of CH2O in Cu-C and Cu-O bonds were
suggested for the formation of (2,4,6-trimethylbenzyl)formate
from the reaction of Cu(PPh3)(2,4,6-Me3C6H2) with para-
formaldehyde.11b As reported by Carmona and co-workers,
reaction of solutions of 1 stirred over paraformaldehyde results
in initial insertion of OCH2 into the Ni-C(alkyl) bond to give
good yields of 2.6 However, as shown in Scheme 2, solutions
of 2 are unstable in the presence of paraformaldehyde. Formal
sequential CH2O insertion into Ni-O bonds occurs slowly when
2 is stirred (23 °C, 3 days) with a suspension of paraformal-
dehyde, giving formic acid 3-methyl-3-phenylbutyl ester, PhCMe2-
CH2CH2OC(O)H (9), which incorporates two CH2O units, and
formic acid (3-methyl-3-phenylbutoxy)methyl ester, PhCMe2-
CH2CH2OCH2OC(O)H (10), which incorporates three CH2O
units, in 20 and 41% yields, respectively. Products incorporating
more than 3 equiv of formaldehyde were not detected, consistent
with slow insertion steps and increasingly faster rates of â-H
elimination as the size of the metallacycle increases (a seven-
membered ring for 2 and nine- and eleven-membered rings for
the parents of 9 and 10, respectively). The instability of the
oxametallacycle intermediates might also be a consequence of
the large ring sizes prohibiting dimerization analogous to 2.
In summary, the seven-membered Ni(II) oxametallacycles
2-4 undergo oxidatively-induced C,O-reductive-eliminations
to give 4,4-dimethylchroman, whereas thermolysis of these
complexes results in â-H elimination with formation of 3-meth-
yl-3-phenylbutyraldehyde. Examples of aldehyde insertion into
the Ni-O bonds of these complexes were observed, including
insertion of 2 equiv of CH2O with 2.
A reasonable reaction sequence accounting for the formation
of 7 is shown in Scheme 1. The overall transformation leading
to production of 7 is a formal insertion of 6 into the Ni-O
bond of 3 followed by â-H elimination and C,H-reductive-
elimination to give the ester. This is effectively a type of Ni-
mediated Tishchenko reaction (which typically gives esters from
coupling of aldehydes or primary alcohols).10 Aldehyde
couplings related to that in eq 4 are addressed subsequently with
regard to reactions of formaldehyde.
Prolonged thermolysis of the bpy derivative 4 yields aldehyde
6 along with a significant amount of the primary alcohol
3-methyl-3-phenylbutanol (8), as shown in eq 5. That 4 is more
thermally robust than either 2 or 3 is probably a consequence
of the greater ease in forming three-coordinate Ni complexes
that are subject to elimination or insertion reactions (see above)
for these phosphine-containing compounds than for the more
rigid and less labile bpy derivative. Although the source of
the protons in the formation of 8 has not been established, the
alcohol possibly derives from homolytic Ni-O bond-breaking
followed by H-abstraction. In this reaction, only traces of 7
are observed.
Acknowledgment. We are grateful to the National Science Founda-
tion (CHE-9505692) for financial support of this research.
Supporting Information Available: Synthetic, spectroscopic, and
analytical data (5 pages). See any current masthead page for ordering
and Internet access information.
The observation of aldehyde (6) insertion into the Ni-O bond
of 3 to give, ultimately, an ester led us to reinvestigate the
reactivity of 1 with formaldehyde. Insertions of CH2O into
JA9714999
(11) (a) Wayland, B. B.; Woods, B. A.; Minda, V. M. J. Chem. Soc.,
Chem. Commun. 1982, 634. (b) Leoni, P.; Pasquali, M. J. Organomet. Chem.
1983, 255, C31. (c) Maatta, E. A.; Marks, T. J. J. Am. Chem. Soc. 1981,
103, 3576. (d) Tikkanen, W. R.; Petersen, J. L. Organometallics 1984, 3,
1651. (e) Goeden, G. V.; Caulton, K. G. J. Am. Chem. Soc. 1981, 103,
7354. (f) Wei, M.; Wayland, B. B. Organometallics 1996, 15, 4681.
(10) (a) Villani, F. J.; Nord, F. F. J. Am. Chem. Soc. 1947, 69, 2605. (b)
Tsuda, T.; Habu, H.; Saegusa, T. J. Chem. Soc., Chem. Commun. 1974,
620. (c) Stapp, P. R. J. Org. Chem. 1973, 38, 1433. (d) Murahashi, S.-I.;
Naota, T.; Ito, K.; Maeda, Y.; Taki, H. J. Org. Chem. 1987, 52, 4319.