C H A P T E R

20
Application of Microwave Irradiation
in the Synthesis of P-Heterocycles
György Keglevich
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics,
Budapest, Hungary

O U T L I N E

1. Introduction 559 4.  Phospha-Michael Reactions 564

2.  Functionalization of Cyclic Phosphinic Acids 560 5.  Kabachnik–Fields Reactions 566
2.1 Direct Esterification and Amidation of Cyclic
6.  Concluding Remarks 568
Phosphinic Acids 560
2.2  Alkylating Esterification of Cyclic Phosphinic Acids 562 References568
3. Diels–Alder Cycloadditions, Fragmentation-Related
Phosphorylations, and Inverse Wittig-Type Reactions563

1. INTRODUCTION

The P-heterocyclic research has been continuing for almost three decades in the Keglevich group that commenced
after a postdoctoral fellowship under the guidance of L.D. Quin at Duke University (Durham, North Carolina).
The Hungarian research group elaborated the ring expansion of easily available 3-phospholene 1-oxides to simple
6-membered derivatives, like 3-phosphabicyclo[3.1.0]hexane 3-oxides and 1,2-dihydrophosphinine 1-oxides [1–3].
Then, other P-heterocyclic derivatives such as 1,2,3,6-tetrahydrophosphinine oxides, 1,2,3,4,5,6-hexahydrophosphi-
nine oxides, aromatic phosphinines, bridged phosphabicyclo[2.2.2]octadiene, and -octene derivatives along with
other representatives were also synthesized [4,5]. In collaboration with L.D. Quin, the chemistry of phospholes was
also explored [6–8].
Organophosphorus compounds including P-hetereocycles find applications in synthetic organic chemistry as
reactants, solvents (ionic liquids), catalysts, and P-ligands and, due to their biological activity, also as components of
drugs and plant protecting agents [9–11].
In respect of P-heterocycles, 2- and 3-phospholene oxides may be used as catalysts in the synthesis of carbodi-
imides from isocyanides [12]. Similarly, 2- and 3-phospholene oxides were applied in the catalytic version of the Wit-
tig and the Appel reactions [13–15]. Recently, we have elaborated the optical resolution of 3-phospholene oxides and
a few six-membered derivatives [16–20] that together with the racemic derivatives were used after deoxygenation
as P-ligands in platinum complexes [21–23]. The P2PtCl2-type complexes (where P = P-heterocyclic moiety) showed
interesting regioselectivity in the hydroformylation of styrene [22,23]; however, in case of optically active P-ligands,
the enantioselectivity was quite low [22,23]. A part of the P-heterocycles synthesized by us was tested and a few
exhibited considerable anticancer activity [24].

Green Synthetic Approaches for Biologically Relevant Heterocycles 559

http://dx.doi.org/10.1016/B978-0-12-800070-0.00020-7 © 2015 Elsevier Inc. All rights reserved.
560 20.  APPLICATION OF MICROWAVE IRRADIATION

The use of the microwave (MW) technique in organic syntheses has spread gradually in research laboratories, and
after three decades it knocks at the door of industry. At the beginning (from the 1980s), only domestic MW ovens
were available, but later (from the mid-1990s), different variations of professional MW equipment were developed
and utilized in a variety of syntheses, such as substitutions, additions, eliminations, condensations, acylations, esteri-
fications, alkylations, C–C coupling reactions, cycloadditions, rearrangements, and the formation of heterocycles,
occasionally in multicomponent reactions [25].
The most common benefits from MW irradiation are the considerable shortening of reaction times and the increase
in the selectivities. However, the most valuable benefit is when a reaction can be carried out that is otherwise impos-
sible under traditional thermal conditions. This may be the consequence of a so-called special MW effect [26]. There
are, of course, other advantages as well that will be shown below within the discipline of P-heterocyclic chemistry
that is the part of the dynamically developing organophosphorus chemistry. The utilization of MW irradiation in
organophosphorus chemistry is a relatively new field [27–32]. In this chapter, the MW-assisted reactions described in
the field of P-heterocycles are summarized.

2.  FUNCTIONALIZATION OF CYCLIC PHOSPHINIC ACIDS

2.1  Direct Esterification and Amidation of Cyclic Phosphinic Acids

The most common way to prepare esters (2) is the acid-catalyzed direct esterification of carboxylic acids (1) with
alcohols (Scheme 1). The reaction is reversible, hence the alcohol should be applied in excess and/or the water
formed should be removed by distillation, in most cases, in the form of binary or ternary azeotropes.
However, it is well known that phosphinic acids (3) do not undergo esterification with alcohols to afford phos-
phinates (4) (Scheme 2/A). For this, the esters of phosphinic acids (4) are synthesized by the reaction of phosphinic
chlorides (5) with alcohols in the presence of a base (Scheme 2/B) [9]. Alternatively, they may be prepared by Arbu-
zov reaction (Scheme 2/C) [9].
The generally applied esterification method (Scheme 2/B) suffers from certain drawbacks, especially the use of
relatively expensive P-chlorides (e.g., 5) and also the use of a base to remove the hydrogen chloride formed as the
by-product. Hence, this method is not atomic efficient and environmentally not friendly. It was thus a challenge for
us to try the direct esterification of phosphinic acids with alcohols under MW conditions. It was our delight that a
series of phosphinic acids underwent esterification with alcohols with longer chain at around or above 200 °C on MW
irradiation (Scheme 3) [33–37].
The esterification of cyclic phosphinic acids such as 1-hydroxy-3-phospholene oxides (7 and 8), 1-hydroxy-­
phospholane oxides (11 and 13), and 1-hydroxy-1,2,3,4,5,6-hexahydrophosphinine oxide (15) was carried out in the
presence of c. 15-fold excess of the alcohols in a closed vessel to afford the phosphinates (9, 10, 12, 14, and 16) in
acceptable to excellent (44–95%) yields [33–37]. The method elaborated seems to be of general value. It was found
that the esterification of phosphinic acids is thermoneutral and kinetically controlled, and also represented as an
irreversible process [35].

O H O
R1C + R2OH R1C + H2O
OH OR2
1 2
R1 = alkyl, aryl R2 = alkyl

SCHEME 1  Direct esterification of carboxylic acids.

B
base R1 O
R3OH + P
A − HCl
R1 O R1 O R2 Cl
P 3
+ R OH 5
P
R2 OH − H2O R2 OR3 C OR3
3 4 R2X + R1 P
R1, R2 = alkyl, aryl R3 = alkyl − R3X OR3
6

SCHEME 2  Possibilities for the synthesis of phosphinates.

 2.  Functionalization of Cyclic Phosphinic Acids 561
Thioalcohols could also be used as reaction components with 1-hydroxy-3-phospholene oxides (7 and 8) under
MW conditions. It was not a surprise that the products were thioesters (17) and not esters (9/10) (Scheme 4) [38].
Hence, indeed the alcohol/thioalcohol is phosphinoylated by reaction with the cyclic phosphinic acid and not
the phosphinic acid is alkylated by the alcohol or thioalcohol. Quantum chemical calculations revealed that
the esterification with thioalcohols is rather endothermic (48.5 kJ/mol) and the enthalpy of activation is rather high
(ca. 145 kJ/mol), higher than that is for esterifications (ca. 102 kJ/mol) [38].
After the esterifications and thioesterifications, the direct amidation of cyclic phosphinic acids was also attempted.
The interaction of 1-hydroxy-3-phospholene oxide (7) and 1-hydroxy-phospholane oxides (11 and 13) with primary
amines under MW conditions took place in conversions of ca. 33% (Scheme 5). The amides (18–20) were isolated
with 23–29% yields [37,39].
As compared to the direct esterifications, the amidations had a lower enthalpy of activation (ca. 79 vs ca. 102 kcal/
mol); however, the amidations were significantly endothermic (33 kcal/mol) [39]. It is recalled herein that the
esterifications are thermoneutral [35]. As far as such amidation reactions are concerned, it is the fact that the MW-
assisted reaction of phosphinic acids and amines is of limited use and the traditional method involving the reac-
tion of phosphinic chlorides with amines still remains the method of choice (Scheme 5). During the preparation of
1-amino-3-phospholene oxides (21) by this method, an interesting side reaction was also found to take place yielding
a bis(phosphinoyl) amine (22) (Scheme 6) [40]. However, using appropriate molar ratios and addition techniques,
both the formation of the amino-3-phospholene oxides (21) and that of the bis(products) (22) could be optimized [40].

MW
R2 Me
220−235 °C R2 Me
~3h
+ R1OH (1)
P P
O OH O OR1
7 (R2 = H) 9 (R2 = H)
8 (R2 = Me) 10 (R2 = Me)

MW
Me Me
~ 230 °C
~ 3.5 h
+ R1OH (2)
P P
O OH O OR1
11 12

Me Me Me Me Me Me
~ 235 °C
~5h
+ R1OH + (3)
P P P
O OH O OR1 O OR1
13 14A 14B

Me ~ 235 °C Me
~5h
+ R1OH (4)
P P
O OH O OR1
15 16
R1 = nBu, C5H11, iC5H11, C8H17, iC8H17, C12H25

SCHEME 3  MW-assisted direct esterification of cyclic phosphinic acids.

MW MW
R1 Me 200 °C R1 Me 200 °C R1 Me
R2SH R2SH
P − H2S P − H2O P
O OR2 O OH O SR2
9/ 10 7 (R1 = H) 17
8 (R1 = Me) R2 = nBu, nPent

SCHEME 4  The reaction of 1-hydroxy-3-phospholene 1-oxides with thioalcohols.

562 20.  APPLICATION OF MICROWAVE IRRADIATION

MW
~220 °C/6-8 bar
R3NH2
R1 O (excess) R1 O
P P
R2 OH R2 O
7, 11, 13 R3NH3

SOCl2 26 °C − H2O
CHCl3

R3NH2
R1 O R1 O
NEt3
P P
R2 Cl PHMe R2 NHR3
− HCl
5 18−20

R1 Me Me Me

R2 , ,
Me
R3 = nHex, cHex, Bn

SCHEME 5  The amidation of phosphinic acids.

Me

P
Me 26 °C Me RNH2 O NHR
SOCl2 Et3N 21
P CH2Cl2 P PhMe
O OH O Cl Me Me
7
P P
O NR O
22

SCHEME 6  The amidation and imidation of 1-chloro-3-phospholene 1-oxide by reaction with amines.

The derivatization of cyclic phosphinic acid demonstrates well when the use of the MW technique is advanta-
geous. Our examples confirmed that MW irradiation may be suitable to promote reactions having relatively high
enthalpy of activations. The statistically occurring local overheating effect [26] enhances to overcome the high bar-
rier. It is, however, a criterion that the reaction should be at least thermoneutral and not endothermic. This was the
case with the direct esterification of cyclic phosphinic acids [35]. Regarding thioesterifications and amidations, the
success was only partial due to the significant extent of endothermicity of such reactions [38,39]. In summary, it can
be said that the esterification, thioesterification, and amidation of phosphinic acids are the reactions that do not take
place on conventional heating, but can be completely or partially achieved under MW conditions.

2.2  Alkylating Esterification of Cyclic Phosphinic Acids

O-Alkylations of phenol derivatives were studied in solid–liquid phase using K2CO3 as a base under MW condi-
tions, and it was observed that the O-selectivity was enhanced in the presence of triethylbenzylammonium chloride
(TEBAC) as the phase-transfer catalyst, thereby indicating the phenomenon of synergism in respect of MW irradia-
tion and the phase-transfer catalyst [41–43].
Then, we wished to make use of the MW technique in the alkylating esterification of cyclic phosphinic acids such
as 1-hydroxy-3-phospholene oxides (7 and 8), 1-hydroxy-phospholane oxides (11 and 13), and 1,2,3,4,5,6-hexahydro-
phosphinine oxide 15. The cyclic phosphinic acids 7, 8, 11, 13, and 15 were reacted with a series of alkyl halides in the
presence of K2CO3 under solvent-free and MW conditions (Scheme 7). It was found that the application of TEBAC
was beneficial, when alkyl halides with normal or decreased reactivity, such as ethyl iodide, n-propyl bromide,
n-butyl bromide, and isopropyl bromide were the reactants. At the same time, when an alkyl halide with increased
reactivity, such as benzyl bromide, was used, there was no need for the catalyst [34,44,45].
 3. Diels–Alder Cycloadditions, Fragmentation-Related Phosphorylations, and Inverse Wittig-Type Reactions 563
MW
2 100 °C
R Me
TEBAC R2 Me
K2CO3
+ R1X (1)
P no solvent P
O OH O OR1
7 (R2 = H) 9 (R2 = H)
8 (R2 = Me) 10 (R2 = Me)
MW
120 °C
R2 Me
TEBAC R2 Me
K2CO3
+ R1X (2)
P no solvent P
O O 1
OH OR
11 (R2 = H) 12 (R2 = H) [as 2 isomers]
13 (R2 = Me) 14 (R2 = Me) [as 3 isomers]
MW
120 °C
Me TEBAC Me
K2CO3
+ R X 1 (3)
P no solvent P
O OH O OR1
15 16 [as 2 isomers]
R1 = Et, nPr, iPr, nBu, Bn
X = Br, I

SCHEME 7  Alkylating esterification of cyclic phosphinic acids.

However, in the case of thermally unstable cyclic phosphinic acids, such as 3-hydroxy-3-phosphabicyclo[3.1.0]-
hexane 3-oxide and 1-hydroxy-1,2-dihydrophosphinine 1-oxide derivatives, the MW-assisted method was not pre-
ferred due to side reactions [46].

3.  DIELS–ALDER CYCLOADDITIONS, FRAGMENTATION-RELATED

PHOSPHORYLATIONS, AND INVERSE WITTIG-TYPE REACTIONS

The 1,2-dihydrophosphinine oxides are versatile intermediates [4,5] and are suitable to take part in Diels–Alder
reaction with different dienophiles, like N-phenyl maleimide and dimethyl acetylenedicarboxylate (DMAD) [47].
These cycloadditions were also performed on MW irradiation in the absence of any solvent. Starting from the
1-­phenyl-dihydrophosphinine oxide (23), the reactions were 25 times faster as compared to the thermal variations,
and the valuable cycloadducts 2-phosphabicyclo[2.2.2]octene 24 and 2-phosphabicyclo[2.2.2]octadiene 25 were
obtained in excellent yields with high purity (Scheme 8) [48].
It was also observed that in case the cycloadditions were performed in solvents, the addition of onium salts
(e.g., TEBAC) had an accelerating effect on the rate that is the consequence of the MW-absorbing ability of the
onium salts [49].

MW MW
110 °C/30 min 110 °C/ 30 min
O CO2Me
O
Ph P N Ph O
Me Cl Ph P
O CO2Me
Cl H O Me Me
(2 eq.) (3 eq.)
Cl CO2Me
H
N no solvent no solvent
P
Ph O CO2Me
Ph
O 23
24 (96%) 25 (95%)

SCHEME 8  Diels–Alder reactions of a 1,2-dihydrophosphinine oxide.

564 20.  APPLICATION OF MICROWAVE IRRADIATION

O MW
Ph P 200 °C /1 h
ArOH O
Me IL
Cl CO2Me Ph P Me
Me
OAr
Cl CO2Me 26
CO2Me
25
Ar = Ph, 4-MePh, 4-ClPh CO2Me
IL = [bmim][BF4] or [bmim][PF6]

SCHEME 9  Fragmentation-related phosphorylation of phenols.

150 °C, ∆ 150 °C, ∆

CO2Me CO2Me
O Cl
Ar P Cl Me
Me CO2Me Me CO2Me
Cl CO2Me P
MeO2C
P Ar
CO2Me O Ar
MeO2C O
29 27 28

SCHEME 10  Inverse Wittig-type reaction instead of Diels–Alder cycloaddition.

The bridged 2-phosphabicyclo[2.2.2]octene (24) and -octadiene (25) derivatives may be regarded precursors of
low-coordinated fragments, as on thermal or photochemical effect, the bridging YP(O)CH2 moiety is ejected that
phosphorylates the nucleophile (alcohol, phenol, or amine) added to the mixture prior to fragmentation [47]. Well,
this kind of fragmentation-related phosphorylations could also be performed on MW irradiation. In our experi-
ments, 2-phenyl-2-phosphabicyclo[2.2.2]octadiene (25) was used as precursor, and phenols as the trapping agents. It
was found that an ionic liquid (e.g., [bmim][BF4]) as the reaction medium was advantageous (Scheme 9) [50].
It was a surprising experience that heating at a temperature above 150 °C, the outcome of the interaction of
1-(2,4,6-trialkylphenyl-)1,2-dihydrophosphinine oxides (27) with DMAD followed another route yielding the cor-
responding β-oxophosphorane derivative (28). This reaction is called as inverse Wittig reaction (Scheme 10) [51,52].
This new reaction proved to be general, as took place also with the 1-aryl-3-phospholene 1-oxides (30), 1-aryl-phos-
pholane oxides (32), and 1-aryl-1,2,3,4,5,6-hexahydrophosphinine oxides (34). The reactions were, however, rather
slow with a reaction time of 7–14 days at 150 °C depending on the substituents. It was observed that the reaction time
of such conversions (i.e., 30/32/27/34 → 31/33/28/35) at 150 °C decreased dramatically under MW conditions; the
reactions were almost complete after 3–6 h of irradiation (Scheme 11) [53–55]. Thus, MW application resulted in an
average of 50-fold rate enhancement. In addition, the polymerization of DMAD was also suppressed increasing the
yield and facilitating the purification process.

4.  PHOSPHA-MICHAEL REACTIONS

Phospha-Michael reactions are useful to establish a P–C bond. The addition of >P(O)H species (e.g., dialkyl phos-
phites and secondary phosphine oxides) at the end of electron-poor double bonds may be facilitated by bases, like
NaOR, NaOH, or DBU [56]. The addition of P-heterocyclic nucleophiles was also studied. Dibenzo[c.e][1,2]oxa-
phosphorine oxide (36) added easily on the double bond of methyl vinyl ketone under MW conditions in the absence
of any solvent (Scheme 12) [57].
The MW-assisted phospha-Michael reaction was then extended to the addition of dialkyl phosphites, a phenyl-
H-phosphinate and diphenylphosphine oxide to maleic derivatives, N-substituted maleimide, and maleic acid anhy-
dride giving rise to >P(O)-substituted succinic derivatives (38 and 39) (Scheme 13) [58].
The next efforts were directed to obtain precursors of bidentate P-ligands. In connection with the synthesis of the pre-
cursor of LuPhos and its Pt complex [59], the addition of diphenylphosphine oxide to 1-phenyl-2-phospholene 1-oxide
(40) was studied under MW conditions. The MW-assisted addition of other >P(O)H species was also investigated. It
was found that in most of the cases, the reaction was not selective under MW irradiation (Scheme 14). The traditional
activation of the >P(O)H species by Me3Al followed by the addition of the anion so formed led to “clean” reactions [60].
 4.  Phospha-Michael Reactions 565
Me MW Me
1 CO2R3 150 °C 1
R R
3−6 h
P + P CO2R3 (1)
O
CO2R3
R1 R2 R1 R2 O CO2R3
30 31
R1 iPr tBu Me R3 = Me, Et
iPr
R2 Me Me

Me MW Me
CO2Me 150 °C
R1 R1
3−6 h
P + P CO2Me (2)
O
CO2Me
R1 R2 R1 R2 O CO2Me
32 R1, R2 as above 33

Cl Cl
Me MW Me
CO2R3 150 °C
3h
P + P CO2R3 (3)
O
CO2 R3
O CO2R3
27 R3 = Me, Et 28
(Ar = 2,4,6-tri-isopropylphenyl)

Me MW
CO2Me 154 °C
R R
3−6 h
P + P CO2Me (4)
O
CO2Me
R R R R O CO2Me
34 R = iPr, Me 35

SCHEME 11  Inverse Wittig reactions with other P-aryl heterocycles.

MW
130 °C
+ CH2 CH C CH3
O solvent-free O
P O P
O H O CH2 CH2 C CH3
36 O
37

SCHEME 12  Phospha-Michael addition of dibenzo[c.e][1,2]oxaphosphorine oxide (DOPO) to methyl vinyl ketone.

O
O MW Y1 O
P
Y1 O 120−175 °C/2.5−3 h Y2
N Z + P N Z (1)
Y2 H solvent-free*
O O
Y1 MeO 38
Z = Ph, Me EtO Ph Ph
Y2 EtO MeO EtO Ph

O
O MW O
Y2P
120−175 °C/3 h
O + Y2P(O)H O (2)
solvent-free*
O O
39
Y = EtO, Ph
* in case of Y1 = Y2 = Y = Ph, acetonitrile was used as the solvent
SCHEME 13  Phospha-Michael reactions between >P(O)H species and maleic derivatives.
566 20.  APPLICATION OF MICROWAVE IRRADIATION

O
PY2
MW
180−240 °C
+ Y2P(O)H
P no solvent P
O Ph O Ph
40 41 (47−88%)
Y = EtO, MeO, Ph

SCHEME 14  Phospha-Michael reactions with 1-phenyl-2-phospholene 1-oxide.

Cl O Cl O
Me Me3Al Z2P Me H2 /Pd Z2P Me
+ Z2P(O)H
CHCl3 P
P P
O Y O Y O Y
42 Y = Ph, EtO 43 44
Z = Ph, EtO, MeO

SCHEME 15  Phospha-Michael additions with 1,2-dihydrophosphinine 1-oxides.

O Cl
Cl .. Cl
Cl3SiH (2 eq.) Ph2P Me
Ph2P Me Ph2P Me
pyridine (PhCN)2PtCl2
P
P ..P PhMe
Ph
O Ph Ph Pt
Cl
45 46 Cl 47
O
Cl3SiH (2 eq.) .. Ph2P Me
Ph2P Me Ph2P Me
pyridine (PhCN)2PtCl2
P
P ..P PhMe
Ph
O Ph Ph Pt
Cl
48 49 Cl 50

SCHEME 16  The conversion of 3-phosphinoyl-phosphinine derivatives to cis-chelate Pt complexes.

The synthesis of another kind of bidentate P-ligand was based on the addition of >P(O)H species at the end of
the α,β-double bond of 1,2-dihydrophosphinine oxides (42). As the double bond was not too reactive, the activa-
tion of the >P(O)H reagent by Me3Al was necessary prior to the addition to obtain the 3-phosphono- ((RO)2P(O)-),
3-phosphinoyl- (Ph2P(O)-), and other related ((EtO)PhP(O)-)1,2,3,6-tetrahydrophosphinine oxides (43) (Scheme
15) [61,62]. Under MW irradiation, there was no reaction. The 3-substituted-1,2,3,6-tetrahydrophosphinine oxides
(43) were converted to the fully saturated 1,2,3,4,5,6-hexahydrophosphinine oxides (44) by catalytic hydrogena-
tion (Scheme 15) [63,64].
The 3-phosphinoyl-1-phenyl-1,2,3,6-tetrahydrophosphinine oxide (45) and the 3-phosphinoyl-1-phenyl-
1,2,3,4,5,6-hexahydrophosphinine oxide (48) were converted to the corresponding cis-chelate Pt complexes 47
and 50, respectively, after double deoxygenation followed by complexation by dichlorodibenzonitrile platinum
(Scheme 16) [65,66].

5.  KABACHNIK–FIELDS REACTIONS

In another field, potentially bioactive α-aminophosphonates (51-1) and α-aminophosphine oxides (51-2) were syn-
thesized by the solventless and catalyst-free MW-assisted Kabachnik–Fields (phospha-Mannich) condensation of
primary amines, aldehydes/ketones, and >P(O)H species. Earlier preparations utilized special catalysts (e.g., BiNO3
[67], phthalocyanine [68], and Lantanoid(OTf)3 [69]) that cannot be regarded eco-friendly species. We proved that
under MW conditions, there is no need for any catalyst. Moreover, the syntheses can be carried out without the use
of a solvent (Scheme 17) [70].
 5.  Kabachnik–Fields Reactions 567

O MW R2 O
O Y 80−120 °C/ 20−40 min Y
R1NH2 + + HP R1NH C P
C Y Y
R2 R3 R3
51
R1 = Ph, Bn Y = EtO, MeO, Ph
R2 H Me
R3 Ph Ph

SCHEME 17  Catalyst-free Kabachnik–Fields reactions.

O MW O
R1 80 °C R1
NH + (CH2O)n + HPY2 N CH2 PY2
no solvent
R2 R2
52

R1 =
Me O Cl N
R2 =
Y = EtO or Ph

SCHEME 18  A heterocyclic variation of the Kabachnik–Fields reaction using cyclic amines.

Me O O MW Me O O
Y O 120 °C, 1.5−2 h
+ (HCHO)n + O
R P R Y
NH2 Y H no solvent NH CH2 P
Y
O 53 O 54
R = Me, Ph Y = OMe, OEt, OBu, Ph 74−98%

SCHEME 19  Another heterocyclic variation of the Kabachnik–Fields reaction.

MW O
O O 55 °C R1
R1R2NH + (CH2O)n + P N CH2 P O
CHCl3
H O R2 O
55 56

R1 =
O Me Cl N
R2 =

SCHEME 20  A heterocyclic variation of the Kabachnik–Fields reaction using a heterocyclic P-reagent.

O MW O
Y 100 °C /1 h Y
RNH2 + 2 HCHO + 2 HP RN CH2P
Y Y 2
R = nPr, nBu, cHex 57
Y = EtO, MeO, Ph
SCHEME 21  Double Kabachnik–Fields reaction.

The Kabachnik–Fields condensations were then carried out with a series of heterocyclic amines, such as pyrro-
lidine, piperidine derivatives, morpholine, and piperazine derivatives along with paraformaldehyde and diethyl
phosphite or diphenylphosphine oxide as the other reagents (Scheme 18) [71].
In another version, amino-2H-pyran-2-ones (53) were used as the starting materials to afford interesting N-hetero-
cyclic α-aminophosphonates or α-aminophosphine oxides (54) (Scheme 19) [72,73].
Finally, the phospha-Mannich condensation of 1,3,2-dioxaphosphorine 2-oxide (55) paraformaldehyde and sec-
ondary amines, including five- and six-membered N-heterocycles, was utilized to make available novel heterocyclic
derivatives (56) (Scheme 20) [74]. In these cases, a solvent had to be used.
Double Kabachnik–Fields condensations were also elaborated applying two equivalents of the formaldehyde and
the >P(O)H species to one equivalent of the primary amine (Scheme 21) [75–77].
568 20.  APPLICATION OF MICROWAVE IRRADIATION

80 °C 26 °C CH2 PPh2
O
Ph PhSiH3 Ph Pt(NCPh)2Cl2
RN CH2P RN CH2P RN PtCl2
Ph 2 C6H6 Ph 2 C6H6
CH2 PPh2
58 59
60

SCHEME 22  The synthesis of ring platinum complexes from bis(phospha-Mannich) products.

Bis(phosphinoylmethyl)amines (58) are useful precursors of bidentate P-ligands (59) obtained after double deoxy-
genation by silanes, e.g., trichlorosilane that could be used for the synthesis of ring platinum complexes (60) by reac-
tion with dichlorodibenzonitrile platinum (Scheme 22) [75–78]. Ring Pt complexes are special heterocycles that may
be regarded potential catalysts in homogeneous catalysis.

6.  CONCLUDING REMARKS

This chapter summarizes MW-assisted syntheses of a variety of P-heterocycles of potential biological importance.
The reactions comprise the P-functionalization of cyclic phosphinic acids involving direct esterification, thioesterifi-
cation, and amidation, as well as alkylating esterifications, Diels–Alder cycloadditions, fragmentation-related phos-
phorylations, inverse Wittig-type reactions, phospha-Michael reactions, and Kabachnik–Fields condensations. In a
few cases, preparations of N- or O-heterocyclic organophosphorus compounds are also presented. MW-assisted reac-
tions were generally found to take place within shorter reaction times, and are more selective and efficient. However,
the most valuable benefit is when a reaction can be carried out that is otherwise impossible under traditional thermal
conditions. This may be the consequence of the so-called special MW effect.

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