.10029780470638859.conrr643 [603823]

643
Vilsmeier Formylation
(Vilsmeier-Haack Reaction,
Vilsmeier Reaction,
Vilsmeier-Haack Formylation)
A. GENERAL DESCRIPTION OF THE REACTION
This reaction was first reported by Vilsmeier and Haack in 1927.1It is a
formylation of an electron-enriched aromatic or heterocyclic compound using N,N-
disubstituted formamide (e.g., DMF) as the acylating agent in the presence of an
activating reagent, such as POCl 3. Therefore, this reaction is generally known as the
Vilsmeier formylation,2Vilsmeier-Haack reaction,3Vilsmeier reaction,2d,2h,3i,3x,4or
Vilsmeier-Haack formylation.3nn,3oo,5In addition, this reaction has also been referred
to as the Vilsmeier acylation,3cc,6Vilsmeier-Haack-Arnold reaction,7Vilsmeier-Haack
aroylation,3ooVilsmeier-Haack acylation,3cc,3rr,8Vilsmeier-Haack condensation,3oo,3rr,9
or Vilsmeier-Haack synthesis.10Likewise, the combination of an N,N-disubstituted for-
mamide and an activating reagent3i,4p,5cor the complex of iminium salt formed from
formamide and the activating reagent3i,11is referred to as a Vilsmeier complex,12Vilsmeier
reagent3i,4p,11or Vilsmeier-Haack reagent.3mm,5c
This reaction is applicable only for aromatics that are more reactive than benzene,5b
such as the benzenes activated by an N,N-dimethylamino group and heterocycles, includ-
ing pyrroles,3oo,3rr,8a,13carbazoles,3qq,14indoles,2d,2j,2dd,3iacridines,3mand ferrocenes.15
In addition, the Vilsmeier formylation has a similar trend of regioselectivity as observedin the Friedel-Crafts Acylation , which primarily depends on the electron density of the
attacked site on the substrate. For example, among the annulated furans, thiophenes, andpyrroles, indoles are the most active heterocyles to undergo the formylation at the 3-position, unless it is blocked by an existing group.
3iHowever, benzo[b]thiophene forms
2872Compr ehensive Organic Name Reactions andReagents, byZerong Wang
Cop yright ©2010 John Wiley&Sons, Inc.

GENERAL REACTION SCHEME 2873
the formylated product in a poor yield;5bwhereas 4-methyl-, 4-methoxy-, 4-hydroxy-,
and 4,4/prime-dimethoxystilbenes are found to be inert to the Vilsmeier formylation, leading
to the recovery of starting materials.12On the other hand, the benzene ring can be eas-
ily formylated when the ring is activated by complexing with Mn(CO) 3;7ain contrast,
1-phenyl-2-ethoxycarbonyl-3,4-dimethylphosphole, the analogue of pyrrole, is inactive for
the Vilsmeier formylation when it is complexed with Mn(CO) 3, and the substitution of one
CO by a phosphine ligand in phosphacymantrenes restores the reactivity of the phospholyl
moiety toward the electrophilic attack of the Vilsmeier reagent.16Similarly, porphyrin rings
can be formylated when they are activated via coordination with nickel(II),17copper(II),18
Pd(II), Pt(II), Zn(II), Cr(III), Mn(III), Fe(III), Al(III), Si(IV), or Pt(IV) cation.2u
Besides the activated aromatics and heteroaromatics, simple olefins when activated by
a strong electron-donating group, also undergo the Vilsmeier formylation, such as vinyl
ethers,19O-silylated enolates of carboxylic esters,2vand 3-(dimethylamino)acroleins.2xIn
addition, even aliphatic ketones or aldehydes can be formylated through this reaction, via
the intermediate of enols or vinyl ether in the presence of a strong activating reagent (e.g.,
POCl 3). For example, propionaldehyde diethyl acetal is converted into 3-ethoxy-2-methyl-
acrolein by DMF/POCl 3,20and glutarimides and indoline-2-ones are transformed into
2,6-dichloro-3,5-diformyl-1,4-dihydropyridines3jjand 2-chloro-3-formyl indoles,3irespec-
tively. Other cycloalkanones3mm,21can be converted into 2-chloro-vinyl aldehydes in a
similar manner, and such transformation is also known as chloroformylation.3mmThe
feasibility for the formylation of olefinic moieties is also evidenced when the olefinic
moiety is conjugated to an aromatic or heteroaromatic ring, by which the formyla-
tion takes place at the olefinic component rather than the aromatic part, probably due
to the higher degree of electron density. For example, the Vilsmeier formylation of 4-
N,N-dimethylaminostilbene yields 4- N,N-dimethylamino- α-phenylcinnamaldehyde and
4-N,N-dimethylamino-3-formyl- α-phenylcinnamaldehyde,12and the corresponding reac-
tion of vinylporphyrins and chlorins22leads to the formation of products with the formyl
group preferentially at the terminal carbon of the vinyl group instead of the macrocyclic
mesoposition.13
Furthermore, other acyl chlorides, such as oxalyl chloride,2jphosgene,7athionyl
chloride,3ipyrophosphoryl chloride,2q,2sand even cyanuric chloride,19bcan be applied
as the activating reagents too. In addition, the combination of HC(OMe) 3/TFA,18
HC(OMe) 3/SnCl18
4and DMF/(CF 3SO2)2O5chave also been used for this reaction,
and the combination of DMF/(CF 3SO2)2O is especially good for the formylation of
polyaromatic hydrocarbons and mildly activated benzene derivatives.5cAlso, even 3- N,N-
dimethylaminoacrolein can be used as an acylating reagent to introduce the acrolein moiety
onto the aromatics.23Overall, this reaction is a very useful formylation method offering the
advantages of monoformylation,3oothough it also has unavoidable drawbacks such as the
evolution of gaseous HCl and a difficult work-up process.19b
B. GENERAL REACTION SCHEME
NN
CHO1) DMF/POCl 3
2) Hydrolysis

2874 VILSMEIER FORMYLATION
C. PROPOSED MECHANISMS
Although a cation radical has been reported as the intermediate for the Vilsmeier
formylation,5pit is well known that this reaction proceeds via the formation of a chloroi-
minium ion and subsequent electrophilic aromatic substitution.11
D. MODIFICATION
This reaction has been modified using ultrasound24and microwave4l,25to accelerate
the reaction. In addition, a protocol for the solid-phase formylation has been developedto simplify the purification process.
2hMoreover, the application of various acyl chlorides
instead of POCl 3can also be considered as the modifications.
E. APPLICATIONS
This reaction has very broad applications in organic synthesis.
F. RELATED REACTIONS
N/A

CITED EXPERIMENTAL EXAMPLES 2875
G. CITED EXPERIMENTAL EXAMPLES
Reference 26.
A mixture of 10.0 mL DMF and 1.5 mL POCl 3(16.4 mmol) was stirred at 0◦C under
argon for 10 min to form the Vilsmeier reagent; 5.16 mL of the solution (1.08 eq.) wastransferred to a solution of 1.0 g dipyrrolemethane (6.84 mmol) in 23.0 mL DMF at 0
◦C
under argon. The resulting mixture was stirred at 0◦C for 1.5 h, then 76 mL saturated
aqueous NaOAc solution was added, and the ice bath was removed. The mixture was thenstirred fo r 4 h and allowed to warm to room temperature. The mixture was extracted with
EtOAc, and the combined organic extracts were washed with brine, dried over MgSO
4,
and filtered. Upon removal of solvent under reduced pressure, a brown oil was obtained.This crude oil was dissolved in 34 mL CH
2Cl2, and treated with 2.85 mL triethylamine
(TEA, 20.5 mmol) and 2.08 g Bu 2SnCl 2(6.84 mmol). The resulting mixture was stirred at
room temperature for 30 min. After removal of the solvent, the resulting oil was purifiedby silica gel column chromatography using hexanes/EtOAc (9:1–1:1) containing 1% TEAas the eluent to afford 338 mg 1-formyl-dipyrrolemethane as a brown solid, in a yield of28%, m.p. 115–116
◦C.
Reference 3i.
To a mixture of 64 µL freshly distilled POCl 3(0.70 mmol) and 350 µL DMF at 45◦C
was added 50 mg indoline-2-thione (0.33 mmol); the reaction mixture was stirred at thesame temperature for 20 min and then cooled to 0
◦C on an ice bath. Under constant stir-
ring, 8.0 mL 29% aq NH 4OH was added dropwise. The resulting solution was allowed to
warm to room temperature and extracted with Et 2O. The combined organic extracts were
dried over Na 2SO4and concentrated to dryness. The crude product was dissolved in 1 mL
pyridine, and 42 mg iodine (0.33 mmol) was added. After being stirred for 60 min at roomtemperature, the reaction mixture was acidified with 10 mL 1.5 M H
2SO4, the resulting
solution was extracted with Et 2O. The combined organic extracts were dried over Na 2SO4
and concentrated to dryness. The residue was purified by silica gel flash column chromatog-raphy using hexanes/EtOAc (4:1) as the eluent to afford 42 mg brassilexin, in a yield of71%, m.p. 140–142
◦C.
Other references related to the Vilsmeier formylation are cited in the literature.27

2876 VILSMEIER FORMYLATION
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