Ni-catalyzed cascade formation of C(sp3)-C(sp3) bonds by cyclization and cross-coupling reactions of iodoalkanes with alkyl zinc halides

DOI: 10.1002/anie.200702528

Source and publish data:

Angewandte Chemie - International Edition p. 8790 - 8795 (2007)

Update date:2022-08-04

Topics:

Authors:

Phapale, Vilas B.

Bunuel, Elena

Garcia-Iglesias, Miguel

Cardenas, Diego J.

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Article abstract of DOI:10.1002/anie.200702528

(Chemical Equation Presented) Two for the price of one: The formation of two C(sp³)-C(sp³) bonds can be achieved in a single operation by sequential cyclization and cross-coupling of alkyl zinc bromides with iodoalkanes containing an alkene group (see scheme). The reaction is catalyzed by [Ni(Py)4CI2] in the presence of tridentate nitrogen ligands, shows a high functional-group compatibility, and seems to follow a radical mechanism.

Full text of DOI:10.1002/anie.200702528

Communications

DOI: 10.1002/anie.200702528

Homogeneous Catalysis

Ni-Catalyzed Cascade Formation of C(sp ) C(sp ) Bonds by

Cyclization and Cross-Coupling Reactions of Iodoalkanes withAlkyl

Zinc Halides**

Vilas B. Phapale, Elena Buæuel, Miguel García-Iglesias, and Diego J. Cµrdenas*

The development of methods for the formation of C(sp )

C(sp³) bonds has become a topic of major interest.^[1]In the

last few years, advances in metal-catalyzed cross-coupling

reactions of alkyl electrophiles (halides and tosylates) with

alkyl metal derivatives have been reported.^[2,3]The first report

on a general and functional-group-tolerant alkyl–alkyl cou-

pling reaction was published by Knochel and co-workers, who

used di(alkyl)zinc reagents and alkyl iodides in a nickel-

catalyzed process. This achievement constituted a milestone

in this type of transformation.^[4,5]Di(alkyl) zinc derivatives

have been used extensively as nucleophiles in many reactions,

including cross-coupling reactions for the formation of other

iodides catalyzed by nickel complexes could give rise to

transformations involving the formation of several alkyl–alkyl

bonds in a single operation, in which 5-hexenyl radicals would

undergo cyclization.^[22]Herein we report our results on the

nickel-catalyzed cyclization of alkyl halides containing an

alkene group which takes place with a subsequent cross-

coupling reaction with alkyl zinc bromides.

We first studied the nickel-catalyzed reaction of iodoace-

tal 1a with commercially available organozinc derivative 2a

(4 equiv; Scheme 1). Under the conditions described by Vicic

types of C C bonds.^[6]In subsequent studies the reaction was

extended to the more stable and convenient alkyl zinc

halides.^[7]More recently, Fu and co-workers reported nickel-

catalyzed alkyl–alkyl coupling reactions of alkyl zinc halides

with secondary iodides and bromides,^[8]as well as the first

catalytic asymmetric cross-coupling reaction of alkyl electro-

philes.^[9]Three-component coupling reactions of alkyl halides,

dienes, and organomagnesium or organozinc reagents have

also been reported.^[10]Alkyl–alkyl Negishi cross-coupling

reactions can also be catalyzed by palladium complexes with

heterocyclic carbene ligands.^[11]

Certain cross-coupling reactions of alkyl electrophiles

with alkyl zinc halides seem to follow a radical pathway.^[12–16]

Vicic and co-workers reported the synthesis and catalytic

activity of radical nickel(I) complexes containing terdentate

nitrogen-based ligands in Negishi coupling reactions.^[17]

Although the precise mechanism is not fully understood,

square-planar alkyl–nickel(I) complexes have been proposed

as the active species.^[18]Cobalt-catalyzed radical cyclizations

of olefin-containing halo ketals followed by coupling with

Grignard reagents have been developed by Oshima and co-

workers.^[19–21]We reasoned that radical reactions of alkyl

Scheme 1. Ni-catalyzed cyclization/cross-coupling reaction.

and co-workers (terpyridine and [Ni(cod)₂] (cod = cycloocta-

1,5-diene) as the catalytic system) the cyclization and coupled

derivative 3a was isolated in 24% yield as a racemic single

diasteroeomer. The yield was lower (19%) when bipyridine

was used. Other Ni precursors (NiBr₂, [Ni(acac)₂(acac =

acetylacetone), NiCl₂) gave poorer results. A higher yield

was observed (57%) when the air and moisture-stable blue

complex [Ni(py)₄Cl₂]^[23](py = pyridine) was used as the

catalyst together with terpyridine. We tried some other

nitrogen-based terdentate ligands based on the pybox skel-

eton. The di-sec-butyl derivative gave the best results (79%),

which is in accord with the results previously observed by

Fischer and Fu in simple cross-coupling reactionss.^[9]The

homocoupled compound derived from the alkyl zinc bromide

was isolated in approximately 10% yield (relative to the

starting nucleophile) in most cases. The use of lower amounts

of the nucleophile led to lower yields.

[*] V. B. Phapale, Dr. E. Buæuel, M. García-Iglesias, Dr. D. J. Cµrdenas

Departamento de Química Orgµnica

Universidad Autónoma de Madrid

Cantoblanco, 28049 Madrid (Spain)

Fax: (+34)91-497-3966

E-mail: diego.cardenas@uam.es

[**] We thank the Ministerio de Educación y Ciencia for financial support

under project CTQ2004-02040/BQU and the MAE-AECI for a

fellowship to V.B.P. We also thank the Centro de Computación

Científica-UAM for computation time.

Supporting information for this article (including experimental data

for new compounds, as well as atomic coordinates and energies for

the calculated stationary points) is available on the WWW under

http://www.angewandte.org or from the author.

In the absence of added ligands or in presence of o-

phenanthroline, 4 was obtained in variable yields along with

its reduction product 5, in which iodine had been replaced by

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hydrogen, probably abstracted from the solvent. Formation of

this compound further supports a radical mechanism, since

the reaction of 1a with BEt₃has been reported to give 4.^[24]

This compound cannot be discarded as a reaction intermedi-

ate in the formation of 3a, since it afforded the coupling

product when subjected to the reaction conditions

(Scheme 2).

previously been reported.^[17a]This prompted us to calculate

the structure of the model methyl–nickel(I) complex con-

taining Me-Pybox for comparison. Optimization at the DFT

level shows a square-planar structure, typical of Ni^IIcom-

plexes, with the singly occupied molecular orbital delocalized

on the ligand, as previously reported for the analogous

complex with terpyridine (Figure 1). Therefore, complex I is

better described as a Ni^IIcomplex with a coordinated anionic

terdentate ligand.^[25]

Scheme 2. Cross-coupling of 4 affords the coupling product 3a.

Figure 1. Optimized structure of complex I showing the ligand-cen-

tered singly occupied molecular orbital.

We have shown that [Ni(py)₄Cl₂] is also an effective

catalyst in simple alkyl–alkyl coupling reactions, and con-

stitutes a more convenient Ni source. A variety of alkyl

iodides, both primary (Table 1, entries 1 and 5) and secondary

(entries 2, 3, and 4), afforded the desired coupling derivatives

in moderate to good yields. Cyclization from citronellyl iodide

(6e; Table 1, entry 5) was not observed.

The reaction of 6a with 2a in the presence of terpyridine

afforded 7a in 63% yield, and thus is as effective as when (S)-

(sBu)-Pybox is used as the ligand in the reaction. The

electronic structure of alkyl–nickel(I)–terpyridine complexes,

which have been proposed as the actual catalysts, has

The cyclization and cross-coupling reaction is general and

can be extended to a wide variety of substrates with different

functional groups. Thus, compound 1a gave good results with

other organozinc reagents (Table 2, entries 2 and 3) and

afforded only one diastereomer. The six-membered-ring

derivative 1b gave better yields in the reactions of several

alkyl zinc bromides, although minor amounts of diastereo-

mers of the main compounds were observed in the H MNR

spectra. The stereoisomers could not be separated by column

chromatography, but were characterized by GC-MS. The five-

membered-ring iodoacetal 1c (Table 2, entries 7 and 8) again

afforded only one stereoisomer. In

contrast, the reaction of ether 1d

was not stereoselective (Table 2,

entries 9 and 10) and the two

possible C-3 epimers were

Table 1: Nickel-catalyzed cross-coupling reactions of alkyl iodides.^[a]

Entry

Substrate

RZnBr

Product

t [h]

Yield [%]

obtained in roughly equimolar

amount. Exocyclic halide 1e was

less prone to cyclization, and the

expected product was obtained in

46% yield (Table 2, entry 11)

together with the derivative result-

ing from the cross-coupling reac-

tion of the iodoalkene with the zinc

reagent without previous cycliza-

tion (36%). In all cases, the bicyclic

products show cis fusion.^[26]

79^[b,c](92:8)

Malonate derivative 1 f also

gave the expected compound

(Table 2, entry 12), although some

direct coupling product without

cyclization was obtained (13%).

Especially interesting are the

results obtained with substrate 1g

(Table 2, entries 13 and 14), since

they open up further applications

for the synthesis of compounds

72^[b]

[a] Conditions: [Ni(py)₄Cl₂] (10 mol%), (S)-(sBu)-Pybox (10 mol%), THF, 238C. [b] Relative stereo-

chemistry was not determined. [c] 64% yield using (S)-(iPr)-Pybox as ligand.

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Communications

Table 2: Nickel-catalyzed formation of two alkyl–akyl bonds by radical cyclization and Negishi cross-

coupling.

containing

pyrrolidine ring.

Ketone and nitrile functional

groups are also compatible with

the reaction conditions, which

widens the scope of the reaction.

Thus, the reaction of 6-iodo-2-hex-

anone and 5-iodopentanenitrile

with 3-pentylzinc bromide under

the standard conditions afforded

the desired coupling products in

approximately 65% yield. Never-

theless, the presence of inseparable

by-products has precluded isola-

tion of the pure compounds. Exper-

imental data and spectra can be

Entry

Substrate

RZnBr

Product

t [h]

Yield [%]

found

the

Supporting

Information.^[27]

Experiments and calculations

were performed to obtain mecha-

nistic information about this pro-

cess. Thus, the reaction of the cis

stereoisomer of 1d (9) under the

standard reaction conditions led to

3d’ with the same yield and stereo-

selectivity (Scheme 3), thus indi-

cating the presence of a common

reaction intermediate for both iso-

mers, presumably the same secon-

dary radical.

83 (92:8)^[a]

When the reaction of 1a, 6a, or

6b was performed in the presence

of 1.1 equiv of the radical inhibitor

94 (97:3)^[a]

TEMPO

(2,2,6,6-tetramethyl-1-

piperidinoxy (free radical)), the

formal coupling product of this

reagent with the radical derived

from 2a was obtained (8, ca. 60%)

together with recovered haloal-

kane (ca. 90%). TEMPO may

react with the alkyl–Ni^I(L₃) com-

plex formed by transmetalation

with the organozinc compound

leading to the product and Ni⁰

(Scheme 4). Comproportion with

81 (93:7)^[a]

dialkyl–nickel(II) derivative

could regenerate the active cata-

lyst, as proposed.^[17a]Nevertheless,

we have not been able to ascertain

the necessary oxidation step that

has to take place to explain the

observed yields of

8 and the

amount of recovered halide.

On the other hand, the reaction

in the presence of di-tert-butylated

hydroxytoluene (BHT) led to sim-

ilar yields for simple cross-coupling

reactions of alkyl iodides 6a, 6b,

and 6d (65, 72, and 71%, respec-

tively). In contrast, partial inhibi-

76 (64:36)^[b,c]

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Angewandte

Chemie

of several radical clocks.^[28]The

Table 2: (Continued)

results are summarized in Table 3.

Taking into account the reac-

tion rates for cyclization (Table 3,

entries 1–3) or ring opening

(Table 3, entries 4 and 5) for the

radicals generated from the corre-

sponding iodides, it can be deduced

Entry

Substrate

RZnBr

Product

t [h]

Yield [%]

81 (57:43)^[b,c]

that the key C C coupling reaction

46^[d]

has a rate comparable to a unim-

olecular reaction and took place in

the range 0.9 10⁷–6.7 10⁷s^À1.

Since

bimolecular process

actually takes place, the intrinsic

reactivity of the intermediates spe-

cies must be even higher. There-

63^[e]

fore, the formation of the C C

bond is not the rate-limiting step.

We have performed calcula-

tions to get insight into the forma-

tion of radicals from Ni^Icomplexes.

Thus, the reaction of model

methyl-Ni^I(terpyridine) (II) with

2-iodopropane proceeds through

transition state TS1 (Scheme 5).

The activation free energy is

only 5.1 kcalmol^À1from an associ-

ation complex in which the iodide

ion interacts with the Ni atom

along the axis perpendicular to

[a] Measured by GC-MS. The minor isomer has the opposite configuration at C3. [b] The relative

configuration shown corresponds to the major isomer. The minor one is the C3 epimer [c] Isomers were

separated by flash chromatography. [d] The coupling product without cyclization is formed in 36% yield

(isolated yields). [e] The coupling product without cyclization is formed in 13% yield (the compounds

could not be separated. Yields are calculated from the H NMR spectrum of the mixture).

the

coordination

plane

3.53 .^[29]The reaction is exoergic (À7.3 kcalmol^À1) and

affords the free-radical and square-pyramidal Ni^IIcomplex

III. Although the calculation level does not allow fully

quantitative conclusions to be drawn, the activation energy is

in accord with a reaction taking place at room temperature.

We have also calculated the transition state for the

reaction of II with 2-iodopropane to give radicaloid iodo and

a dialkyl-nickel(II) complexes containing methyl and isopro-

pyl groups as carbon ligands which would presumably evolve

by reductive elimination. This transition state (not shown; see

the Supporting Information) is 10.2 kcalmol^À1less stable than

TS1, and therefore this alternative pathway can be discarded.

A plausible mechanism for the cyclization/coupling reac-

tion is shown in Scheme 6. Our experimental and computa-

tional results, which are in accord with the previous proposal

for simple coupling reactions, suggest that free radicals (A)

are readily formed from alkyl iodides, and that in some cases

they last long enough to cyclize to intermediates B. If

cyclization is slow, a faster coordination to the Ni^IIcomplex

to give dialkyl–nickel(III) intermediates E would take place.

This species would then undergo reductive elimination to give

the coupling product with regeneration of the Ni^Iactive

species. The effect of BHT is not clear, since it only prevents

the reaction of 1a, but not simple cross-coupling reactions.

Since reduced products have not been detected in the reaction

of 1a in the presence of BHT, our hypothesis is that this

reagent decomposes intermediate Ni^IIcomplexes C when the

radical takes time to cyclize instead of rapidly coordinating to

Scheme 3. Reaction of the cis stereoisomer of 1d gives the same

isomeric ratio.

Scheme 4. Possible mechanism for the formation of 8.

tion was observed for the cascade reaction of 1a. The yields

were variable, thus indicating partial inhibition, but were not

reproducible.

The competition between cross-coupling reactions with or

without previous cyclization in some cases (Table 2, entries 11

and 12), together with the plausible radical nature of the

intermediate species, led us to explore the coupling reactions

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Communications

Table 3: Ni-catalyzed cross-coupling reactions of radical-clock precursors with RZnBr ([Ni(py)₄Cl₂]

(10 mol%), (S)-(sec-Bu)-Pybox (10 mol%), THF, 238C).

the Ni center. Alternatively, radical

B could react with the starting

iodide to give A plus rearranged

compounds such as 4, which would

subsequently couple to the organo-

zinc reagent (Scheme 6, dashed

lines).

Entry

Substrate

RZnBr

Product

k [s^{À1 [a]}

]

t [h]

Yield [%]^[b]

0.1

In summary, we have shown

that two different alkyl–alkyl

bonds can be formed from alkyl

iodides and organozinc reagents in

a process that is triggered by the

formation of radicals in the reac-

tion of iodides with Ni^Icomplexes.

2.3ꢀ10⁵

9ꢀ10⁶

41^[b]

25^[b]

6.7ꢀ10⁷

The key C(sp ) C(sp ) bond for-

mation is a fast process, which can

even compete with cyclization of

carbon radicals. [Ni(py)₄Cl₂] is a

convenient precatalyst for these

transformations. Our calculations

show that the reaction of alkyl–

nickel(I) complexes with iodoal-

kanes is fast and affords free rad-

icals, in accord with the experimen-

tal observations. The wide scope

and functional-group compatibility

of this reaction would allow the

development of novel approaches

to the synthesis of complex mole-

10d

[a] Cyclization or ring-opening rate of the radical formed from 10a–d after homolytic cleavage of the C I

bond. See Ref. [28]. [b] The low yields are probable due to the formation of volatile compounds resulting

from H abstraction from the solvent.

cules based on C(sp ) C(sp ) bond

disconnections.

Received: June 11, 2007

Revised: August 30, 2007

Published online: October 5, 2007

Scheme 5. Calculated transition state (DFT level) for the reaction of alkyl–nickel(I) complex with 2-

iodopropane.

Keywords: C C coupling ·

density functional calculations · homogeneous catalysis · nickel ·

radical reactions

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Chemie

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Sauvage, J.-M. Kern, J. Am. Chem. Soc. 1989 , 111 , 7791 – 7800;

b) C. Dietrich-Buchecker, J. Guilhem, J.-M. Kern, C. Pascard, J.-

P. Sauvage, Inorg. Chem. 1994 , 33 , 3498 – 3502.

[26] The reaction of the bromide analogue of 1a with 2a also led to

3a in 57% yield. The reactivity of bromides, chlorides, fluorides,

and tertiary iodides is under investigation.

[27] The presence of heteroatoms in the substrate is not necessary for

the reaction to take place. Thus, we have performed the cross-

coupling reaction of 1-iodo-3-phenylpropane with 3-pentylzinc

bromide under the standard conditions, which afforded the

expected product in approximately 60% yield. Moreover, the

reaction of 1-(but-3-enyl)-2-iodocyclopentane with the same

organozinc compound gave the corresponding cyclization/cross-

coupling derivative in about 70% yield. Again in these cases,

these low polarity compounds could not be separated from by-

products by column chromatography. Experimental details can

be found in the Supporting Information.

[28] M. Newcomb in Radicals in Organic Synthesis, Vol. 1 (Eds.: P.

Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001, chap. 3.1,

pp. 317 – 336.

[19] a) T. Tsuji, H. Yorimitsu, K. Oshima, Angew. Chem. 2002 , 114 ,

4311 – 4313; Angew. Chem. Int. Ed. 2002 , 41 , 4137 – 4139; b) K.

Wakabayashi, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc. 2001 ,

[29] This association complex has been obtained by optimization

after partial intrinsic reaction coordinate (IRC) calculation (15

cycles with the default Gaussian03 IRC parameters).

Angew. Chem. Int. Ed. 2007, 46, 8790 –8795

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.angewandte.org

8795

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DOI: 10.1002/anie.200702528

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Article abstract of DOI:10.1002/anie.200702528

Full text of DOI:10.1002/anie.200702528

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