Recent Synthesis and Transformation of Vinylphosphonates

Mini-Reviews in Organic Chemistry, 2005, 2, 91-109 91

1570-193X/05 $50.00+.00 © 2005 Bentham Science Publishers Ltd.

Recent Synthesis and Transformation of Vinylphosphonates

Valery M. Dembitsky, Abed Al Aziz Al Quntar, Abdullah Haj-Yehiaa and Morris Srebnik*b

aDepartment of Pharmacy, School of Pharmacy, P.O. Box 12065, Hebrew University of Jerusalem, Jerusalem91120, IsraelbDepartment of Medicinal Chemistry and Natural Products, School of Pharmacy, P.O. Box 12065, HebrewUniversity of Jerusalem, Jerusalem 91120, Israel

Abstract: Vinylphosphonates are an important group of compounds. This review summarizes recentdevelopments in the synthesis and transformations of vinylphosphonates. Owing to the importance ofvinylphosphonates, many different synthetic methods have been developed. Especially useful are variousorganometallic synthetic methods utilizing the chemistry of copper, titanium, zirconium, and lithium, etc. Thetransformations of vinylphosphonates is also described and include expoxidation, cycloaddition, Suzukicoupling, and Diels-Alder reactions.

1. INTRODUCTION

The knowledge of phosphorus compounds has expandedso rapidly that it constitute now a major branch ofchemistry, organic molecules containing phosphorus offerfascinating possibilities for structural, synthetic andmechanistic study [1]. Besides being crucial biomolecules inmetabolic processes, as anticancer, antiviral drugs, immunosuppressives, insecticides, antibacterial, and antifungal [2],vinylphosphonates are an exceedingly important group ofcompounds with important practical applications: e.g. theirderivatives are used as copolymers [3], polymer additives[4], flame retardants [5], are important tools in furtherorganic transformations [6], and are useful in many otherapplications, such as fuel and lubricant additives [7].

2. PREPARATION OF VINYLPHOSPHONATES

2.1. Via Copper Complexes

The chemistry of organocopper(I) reagents has especiallyreceived a great deal of attention regarding cis-conjugateaddition reactions with acetylenic compounds [8]. Additionof the above reagent to acetylenic esters undergo a facileconjugate addition reaction with lithium diorganocuprateswith cis addition taking place exclusively [9]. 1-Alkynylsulfoxides and sulfones also undergo cis-conjugate addition[10].

In contrast, the reactions of organocopper(I) reagents witha number of 1-alkynyl phosphorus compounds have beenobserved in a few cases [11].

Reactions of copper(1)halide complexes of trivalentphosphorus with vinylic halides afforded vinylphosphonates2. The direct formation of the vinylic carbon to phosphorusbond has been accomplished via reaction of vinylic halides 1

*Address correspondence to this author at the Department of MedicinalChemistry and Natural Products, School of Pharmacy, P.O. Box 12065,Hebrew University of Jerusalem, Jerusalem 91120, Israel; E-mail:[email protected]

with copper(1)halide complexes of trialkyl phosphites. Inaddition, formation of varying amounts of vinylic chloridesmay be observed if the reaction is performed by usingvinylic bromides with copper(1)chloride complexes oftrialkyl phosphites. This halogen-exchange reaction may bemade synthetically useful through the employment ofcopper(1)chloride complexes of triaryl phosphites orphosphines (Scheme 1) [12].

X

DB

AP

DB

A

O

OR

OR(RO)3PCuBr +

A = H, PhB =H, PhX = Cl, BrD = H, Ph

1 2

Scheme 1.

Recently, stereo- and regioselective synthesis of 1,2,2-trisubstituted vinylphosphonates 3-9 via organocopper(I)reagents with good yields (82-97%) had been reported,(Scheme 2) [13].

Stereoselective syntheses of mono-, di- and trisubstituteddiethyl alk-1-enyl-phosphonates (10-12) from alkynylphos-phonates have been reported (Scheme 3) [14].

2.2. Via Titanium Complexes

A new method of synthesis of 3-amino-1-alkenylphosphonates was described. It involves the additionof imines to the alkynylphosphonate titanium(II) complexesT2, which are prepared in situ from 1-alkynylphosphonatesand Ti(O-i-Pr)4 /2 equiv of i-PrMgCl. Compounds (T5 a-i)were obtained regio- and stereoselectively in high yields[15]. Various types of imines efficiently reacted with thealkynylphosphonate titanium(II)complex T2, prepared from1-alkynylphosphonates, and Ti(O-i-Pr)4/2 equiv of i-PrMgClto produce the desired 3-amino-1-alkenylphosphonates inhigh yields as shown in Table 1. This one-pot reaction isgeneral and proceeds with aliphatic and aromatic substituentson both the vinylic carbon and the nitrogen atom of theimine, in high yields. Other alkyl-vinylphosphonates T3,

92 Mini-Reviews in Organic Chemistry, 2005, Vol. 2, No. 1Srebnik et al.

RP

OEtO

EtO

nBu

CH3PhTe

P

OEtO

EtO

R2CuMgI

Me2CuMgBrPhTe

nBu

CH3I

P

OEtO

EtO

CH2R2

CH2R2H

P

OEtO

EtO

Me2CuMgBrI2

Br

Me2CuMgBrPhSeBr

nBu

CH3PhSe

P

OEtO

EtO

nBu

nBuTMS

P

OEtO

EtO

nBu

CH2CH3I

P

OEtO

EtO

Me2CuMgBr

Ph2CuLi2IMeI

Et2CuMgBrI2

nBu

PhCH3

P

OEtO

EtO

nBu

CH2 CH3

P

OEtO

EtO

nBu2CuLi2ITMSCl

3

4

5

6

7

8

9

Scheme 2.

R

R1H

P

OEtO

EtO RP

OEtO

EtO

R

HH

P

OEtO

EtO

R

R1R2

P

OEtO

EtO

(R1)2 CuM

H2 O(R1)2 CuM

R2X

H2 /Pd LindmarM = Li, MgCl

10

11

12

Scheme 3.

Table 1. 3-Amino-1-Alkenylphosphonates (T5 a-i) Obtainedfrom Addition of Imines to the Alkynylphos-phonate Titacycles T2

Entry R R1 R2 31P yield Yield

T5a Ph p-tolyl Me 97% 79%

T5b Ph p-MeO-Ph i-Pr 95% 78%

T5c n-Bu Et Bz 95% 80%

T5d n-Bu Ph Bz 98% 85%

T5e n-Bu Ph Ph 95% 75%

T5f n-Bu Ph i-Pr 98% 79%

T5g n-Bu p-MeO-Ph i-Pr 98% 81%

T5h 1-CIPr Ph Ph 95% 70%

T5i 1-CIPr Ph Bz 90% 71%

T4, T6 and T7 also were obtained by tuning of the Ti(O-i-Pr)4/ Grignard reagents (Scheme 4) [16].

2.3. Via Zirconium Complexes

Zirconation of 1-alkynes provides zirconocyles that canbe reacted further to give highly functionalized and complexderivatives. Hydrozirconation of alkynes tovinylzirconocenes followed by transmetallation gives accessto a host of new organometallic reagents that react withvarious electrophiles in a highly specific manner [17].Hydroboration of alkynes followed by Suzuki coupling hasbeen developed over the last ten years into the method ofchoice for the stereospecific synthesis of highly substitutedalkenes [18]. In spite of the great popularity of both thesemethods, it is surprising that they have never been appliedto 1-alkynylphosphonates. 1-Alkynylphosphonates arereadily available by lithiation followed by reaction withchlorophosphates. Subsequent conversion of the metallatedVinylphosphonates by electrophiles would be expected to

Recent Synthesis and Transformation of VinylphosphonatesMini-Reviews in Organic Chemistry, 2005, Vol. 2, No. 1 93

PR

OOEtOEt

Ph HHO

R2

PR

OOEtOEt

IPr O

R2

PR

OOEt

OEt

PhMgBr R2C(O)Cl

Ti

PR

iPrO OiPr

OOEtOEt

NR2

R1

H

PR

OOEtOEt

HR1

PR

OOEtOEt

HR1

H NH

R2

T6

PR

OOEtOEt

HR1

HO R2

Ti(OiPr)4iPrMgCl

CuBrSMe2

R2C(O)Cl

R2C(O)ClR1MgX

iPrMgCl

T2

T3

T4

T5a-i

T7

Scheme 4.

THF

PR

OOEt

OEt

O

OEt

OEt

R

ZrCp2

P R2R1

P

OOEt

OEt

H3O+

R

H H

ZrCp2EtO

R2R

R1

P

O

OEt

P

R2

R

O

EtOEtO

H3O+

R ZrCp2

R2P

R1

OEtO

EtO

R

R2

P OEtOOEt

H3O+

3a R = n-Bu, Yield = 79%.3b R = n-Pent, Yield = 76%.3c R = Cl-Prop, Yield = 63%.3d R = Ph, Yield = 76%.3e R = TBDMSiC3H6 , Yield = 78%

Z1

Z2

Z3 Z4

Z5 Z6

+

+

Cp2ZrCl22 nBuLi

R2 R1 Yield% Yield% Z5 Z6H C4H9 15 68H C5H11 19 60H Ph 11 73H C3H6Cl 20 57C2H5 C2H5 83 <3

R1R1

Scheme 5.

give highly selective and functionalized di- andtrisubstituted vinylphosphonates.

Zirconation of 1-alkynylphosphonates followed byreductive cyclization by Negishi's reagent, Cp2ZrCl2/2 n-

BuLi [19], has been used extensively for the formation ofthree membered zirconacycle Z1 in which after simplehydrolysis furnished cis-vinylphosphonates Z2. Addition ofvarious alkynes to Z1 produced the five Membered ringzirconacylcles Z3, Z4 in which after hydrolysis afforded


PR

OOEt

OEt

THF

R

ZrCp2

P

O

OEt

OEt

RCHO

ZrCp2

O

RP

nBu

OEtO

EtO

ZrCp2

O

RnBu

P

O

EtOOEt

H3O+H3 O+

Bun

P

R

OHO

EtO

EtO

OHR

P

nBu

OEtO

EtO

Z8 Z7

+

Z9Z10

R = Ph, yield, 10%, conversion 98%R = PhCH=CH, 11%, 98%R = 1,4-benzodioxane, 9%, 95%R = p-F-Ph, 11%, 75%R = 1- naphthyl , 12%, 65%R = p-MeO-Ph, 7%, 65%R = C6 H1 3, 8%, 95%R = O-MeO-Ph, <1%, 70%R = 2,4-dichloro-Ph, <1%, 70%

R = Ph, yield, 75%, conversion 98%R = PhCH=CH, 76%, 98%R = 1,4-benzodioxane,71%, 95%R = p-F-Ph, 48%, 75%R = 1- naphthyl, 38%, 65%R = p-MeO-Ph, 38%, 65%R = C6H13 , 70%, 95%R = O-MeO-Ph, 72, 70%R = 2,4-dichloro-Ph, 74%, 70%

Cp2ZrCl22 nBuLi

Scheme 6.

compounds Z5 that have E,E configuration of the doublebonds, and the Z,E compounds Z6, (Scheme 5) [20].

In addition, 1-alkynylphosphonate reacts with Cp2ZrCl2/ 2 n-BuLi to give a three-membered zirconacycle Z1 thatreadily inserts aldehydes. Hydrolysis of the intermediatefive-membered zirconacycles Z7, Z8 leads to two products,Z9 and Z10, (Scheme 6). In the major product, Z10, the

aldehyde inserted into C2 of the zirconacycle, while in theminor product, Z9, the aldehyde inserted into C1.ProductsZ10 obtained in 38-75% isolated yields. Products Z9 areobtained in approximately 1-12%. Essentially, onlycompounds Z9 are produced with ortho-substitutedaldehydes. The regio- and stereochemistry of Z9 and Z10were determined by NMR techniques [21].

Furthermore, the three member ring zirconacycle Z1,insert ketones exclusively at C2 to give the five-memberring zirconacycle phosphonates Z11 , which can behydrolyzed to give 2-(hydroxymethyl)vinylphosphonates,Z12, in excellent yield, (Scheme 7) [22].

The preparation of l-(hydroxymethyl)vinylphosphonatesby the reaction of α-phosphonovinyl carbanions bearing β-

alkylthio, β-alkyloxy and β,β-bis(alkylthio) substituentswith aldehydes has been reported [23]. It should be notedthat α-phosphonovinyl cuprates do not react with oxygenelectrophiles. The present reaction, on the other hand, is verygeneral for both dialkyl-, alkylaryl-, and diarylketones. Theyields are uniformly high [13,14].


ZrCp2

O

RR

P

O

EtOOEt

THF

PR

OOEt

OEt

R1R2CHO

H3O+

R

ZrCp2

P

O

OEt

OEt

R

P

R2

OHO

EtO

EtO

R1

Z11 Z12

R = nBu, R1 = Me, R2 = Ph, conversion 99%

R = nBu, R1 = R2 = Me, conversion 99%

R = nBu, R1 = Me, R2 = nPent, conversion 99%

R = nBu, R1 = iPr, R2 = Ph, conversion 99%

R = Ph, R1 = R2 = Me, conversion 99%

R = ClC3H6, R1 = Me, R2 = Ph, conversion 95%

R = ClC3H6, R1 = C5H11, R2 = Me, conversion 98%

R = ClC3H6, R1 = R2 = Ph, conversion 95%

Z1

Cp2ZrCl22 nBuLi

Scheme 7.

PO(OEt)2R1

PO(OEt)2

R1

R3 OHR2

NaH

.

R3

R2R1

H

PO(OEt)2R1

Li

N(iPr)2

PO(OEt)2R1

N(iPr)2

R3 OHR2

R2 R3

O

LDA

L1

L2

L3

L4

L5

Scheme 8.

2.4. Via Lithium Salts

A sequence of reactions involving conjugate addition oflithium diisopropylamide (LDA) to alkenylphosphonates L1

and subsequent aldol-type reaction of the resultant lithiatedphosphonates L2 with aldehydes or ketones produced L3.(Scheme 8). Further elimination products L4 were produced.It is important to note that L4 is readily converted toallenes, L5 , by treatment with a base under Horner-Wadsworth-Emmons conditions. The conversion of L3 tothe 1-(hydroxymethyl)vinylphosphonates, L4, proceeded ingood to high yields [24].

These results imply that conjugate addition of LDA toL6, enabled the formation of the kinetic anion, L7, which isnot stable and is converted to the thermodynamic allylicanion, L9 , as shown in (Scheme 9). This suggests thataddition of LDA to, L6, in the presence of benzaldehydewould increase the yield of L8, because the initially formedanion, L7, may react rapidly with benzaldehyde before theestablishment of the equilibrium with L9. Thus, addition ofa solution of 1.1 equiv of LDA in THF to a mixture of L6and an equivalent of benzaldehyde in THF afforded, after 1 hat -78 °C, the desired product, L8, in acceptable 73% yieldalong with L11, in 11% yield [24].

2.5. Via Arbusov Reaction

The Michaselis-Arbusov reaction of 2-chlorovinylketones with trialkyl phosphates afforded 3-


PO(OEt)2

Me

PO(OEt)2Me

Li

N(iPr)2

PhCHO

Li

PO(OEt)2Me

PO(OEt)2R1

Ph OH

Li

PO(OEt)2

PhCHO

OHPh

PO(OEt)2

L7 L8

L11

L9

L10

PhCHO

THF, -78, 1h

deprotination

L6

Scheme 9.

C(O)R1

HCl

H

COR1P

P

OR2O

R2O

O

OR2

OR2

P

OR2O

R2OH

H OP

OOR2

OR2

C(O)R1

HP

H

OR2 O

R2O

+ (R2O)3

13

14

15

16

14a. R1 = R2 = CH3, yield, 12%.

14b. R1 = CH3 , R2 = C2H5, yield, 29%.

14c. R1 = R2 = C2H5, yield, 24%.

14d. R1 = CH(CH3)2, R2 = C2 H5 , yield, 27%.

14e. R1 = C6H5, R2 = CH(CH3)2, yield, 40%.

14f. R1 = CH3, R2 = CH(CH3)2 yield, 47%.

14g. R1 = C6H5, R2 = CH3, yield, 40%.

Scheme 10.

oxovinylphosphonates, 14, as well as enolphoshonates, 15,and 3-oxo-1,1-alkanebisphosphonates, 16, (Scheme 10) [25].

2.6. Via Heck Reaction

A facile synthesis of aryl vinylphosphonates 17-23 hasbeen reported based on Heck reaction of aryldiazonium saltsbearing electron-withdrawing or donating groups withvinylphosphonates. A one-pot procedure consisting of Heck

reaction and hydrogenation permits the clean formation ofuseful Wadsworth-Emmons reagents (Scheme 11) [26].

2.7. Via Olefination Reactions

a) Vinylphosphonates were obtained using Petersonreagent, which is generated in situ.33 Products Z, andE-1-alkylidene-3-oxobutylphosphonates 24 wereobtained in good yields (Scheme 12) [27].


N2BF4MeO

P

OOEtOEt

N2 BF4MeO

ClP

OOEtOEt

N2BF4

O2 N

F

P

OOEtOEt

N2BF4MeO

MeO

MeOP

OOEtOEt

N2BF4

Br

P

OOEtOEt

N2BF4I

P

OOEtOEt

N2BF4

COOEt

P

OOEtOEt

MeOP

OOEt

OEt

MeOP

OOEt

OEt

MeO

MeO

MeOP

OOEt

OEt

Cl

P

OOEt

OEt

O2N

F

P

OOEt

OEtI

P

OOEt

OEt

Br

P

OOEt

OEt

COOEt

Pd/CaCO3

Pd/CaCO3

Pd/CaCO3

Pd/CaCO3

Pd/CaCO3

Pd/CaCO3

Pd/CaCO3

23

22

21

20

19

18

17

Scheme 11.

P

OEtOEt

OEtO

EtO

R1P

O

OEtO

EtO

P

O

OEtO

EtO

R1R1 CHO+

24Z 25E

Scheme 12.

b) Acid or base catalyzed demethoxylation of (2-methoxyethyl)phosphonates produced vinylphosphon-ates, 25, in moderate yields (Scheme 13) [28].

2.8. Via Radical Trapping

Vinylphosphonate formation via a novel cyclization-vinyl radical trapping sequence has been reported recently,(Scheme 14). This study provides a novel route to new


EP

OOEt

OEt R H

O

P

ER

H OOEt

OEt

+piperidine

25 60%E = CO2R, SO2Me

Scheme 13.

.

R

.

HOR2

R1

R3

H

H

OR2R1

R3

R

(MeO)3P

(MeO)3P

(MeO)3P

OR2R1

R3

H

(MeO)2(O)P

H

OR2R1

R3

P(O)(OMe)2

R

P(O)(OMe)2

5-exo-dig

.

.

.

R = H, yield 77%R = Me, 88%R = iPr, 70%R = Ph, 65%R = tBu, 0%

26

27 (E)

2 7(Z)R1 = R2 = R3 = H, yield 84%, E/Z = 61:49

R1 = R2 = H, R3 = OEt, 85%, 66:44

R1 = R2 = H, R3 = Ph, 93%, 48:52

R1 = R2 = Me, R3 = OEt, 89%, 99:1

R1 = Ph, R2 = H, R3 = OEt, 74%, 93:7

Scheme 14.

R2

R1

P

OEtO

EtOAOc

R3

COOEt

H2 CN

Ph

Ph

R2

R1

P

OEtO

EtO

R3

COOEtPh

Ph

+

PdLnBase

P1

P1a. R = Me, R1 = R2 = R3 = H, E/Z 85:15

yield, 77%, E/Z = 65:35

P1b. R = Et, R1 = R2 = R3 = H, E/Z 90:10

yield, 74%, E/Z = 77:23

P1c. R = iPr, R1 = R2 = R3 = H, E/Z 93:7

yield, 93%, E/Z = 87:13

P1d. R = R1 = Me, R2 = R3 = H, E/Z 68:32

yield, 90%, E/Z = 76:24

P1e. R = Pr, R1 = R2 = H, R3 = Me, E/Z 90:10

yield, 100%, E/Z = 100:0

Scheme 15.

vinylphosphonates, 26 , and the biologically activemolecules, 27, (Z and E) [29].

2.9. Via Various Other Catalytic Preparations

a) The palladium(0)-catalyzed reaction of 3-acetoxy-1-alkenyl phosphonates with ethyl (diphenyl methylene

amino acetate) and N,O bis(trimethylsilyl) acetamideprovided the precursors of the 2-amino-5-phosphonovaleric acid and related compounds, (P1 a-e), in high yields (Scheme 15) [30].

b) The reaction between 1-acetoxyallylphonates or-phosphinates with dialkyl hydrogen phosphites or


P

OAc

ORO

RO

P3

P2

P

ORO

RO

P

OOR1

OR1

P

ORO

RO

P

OOR1

OR1

+ (R1O)2P(O)HNiCl2, BSA

120 0C

+

Scheme 16.

HR PO

O

O

H

Pd

PO

OR

O

H PO

OMe

OMe+ (MeO)2P(O)H

P5

+Rh, THF

Acetone

20 0C

R = H, Ph, C6H13, tBu P4

Scheme 17.

Br

P6

P

OOROR+ HP(O)(OR)2

KH, CuI

120 0C

Scheme 18.

phenylphosphonous esters in the presence of NiCl2gave a mixture of the corresponding allyl-andvinylphosphonates P2, P3 (Scheme 16) [31].

c) Tanaka et al. studied reactions of alkynes with thephosphonate (4,4,5,5-tetra-methyl-1,3,2l 5-dioxaphospholane 2-oxide), which is most reactivein the addition to multiple bonds. The reactioncatalyzed by Rhodium complexes was shown to becomplementary to that catalyzed by palladium toafford the corresponding vinylphosphonates P4. As aresult, the isomers with E configuration of the doublebond were obtained at room temperature in highyields (Scheme 17) [32].

Reactions with internal alkynes are very difficult tooccur, they take more than 60 h against 13-22 h forterminal alkynes. However, the products P5 areformed in high yield in the presence of Pd catalyst,and the process clearly follows the syn-additionpattern [33].

d) The Cu catalyzed reactions of β-bromostyrenes withdialkylphosphites to obtain compounds possessingsecond harmonic generation (SHG) activity P6 .Strongly polar solvents, KH as a base, and elevatedtemperature are necessary (Scheme 18) [34].

e) Vinylphosphonates P7 were generated in high yieldsby the reactions of triethyl phosphite with alkenylhalides having an alkoxy or diethylamino group onα - position in the presence of nickel catalyst, andanalogous reactions with β-halovinyl ethers or β-haloenamines occur at higher temperature, but theyields of P8 are also fairly high (Scheme 19) [35].

f) (E,E)-1,3-Diiodobutadiene was converted into bis-1,4-(diethoxyphosphinoyl)-1,3-butadiene, P9-P11 inhigh yield (Scheme 20) [36]. Likewise, mono- anddisubstitution products are formed in reactions with1,3-dienyl halides [37].


X

YR

R

Y

R1Br

R

P

YR

R OOEt

OEt

Y

R1P

R

OEtO

EtO

P8

P(OEt)3NiBr2

70-120 0 C

R = H, MeX = Cl, BrY = OR, NR2

P(OEt)3NiBr2

159 0C

R = H, Me, BrY = OEt, pipyridino, morpholino

P7

Scheme 19.

II

NiBr2

110 0C

II

PhBr

PP

OO

OEt

OEt

EtO

EtO

PP

OO

OEt

OEt

EtO

EtO

PhP

OOEt

OEt

+ 2 HP(O)(Et)2

Pd(0), Et3NPhMe

23 0C

+ 2 HP(O)(Et)2

Pd(0), Et3NPhMe

90 0C

95%P9

P10

P11

+ 2 P(OEt)3

Scheme 20.

g) Reactions catalyzed by palladium(II)chloride oracetate also provide almost quantitative yields of thebis-vinylphosphonates products P12 , P13 . Theprocess is highly stereospecific: the configuration ofthe initial alkene is retained in the product. Scheme21 illustrates the reaction with isomeric 1,2-dichloroethenes as an example [38].

H

ClCl

H

Cl

HCl

H P

HP

H

O

O

OEt

OEtEtO

EtO

H

PP

H

O

EtO

EtO O

OEt

OEt

P(OEt)3

Pd(Cl)2

155 0 C

P(OEt)3

Pd(Cl)2

155 0C

P12

P13

Scheme 21.

3. OTHER MISCELLANEOUS METHODS FOR THEPREPARATION OF SPECIFIC VINYLPHOSPHON-ATES

3.1. Z- and E-di-Substituted Vinylphosphonates

The addition of trimethylsilyloxy phosphorus (III)derivatives, generated in situ, to α -haloacrylates andacrylonitriles at room temperature provides a mild, generaland stereoselective route to phosphonoacrylates, 28 (Scheme22) [39].

PH

OR1

R2P

OTMS

R2R1

P

OR1

R2 R3

R3

Hal

TMSCl, Et3 N

CH2Cl2 , 0C

28Scheme 22.


P

OEtO

EtOCN

NTs

R

P

OEtO

EtOCN

R+DBU, THF

- 30 0C

29 30

30a. R = C6H5, yield, 72%30b. R = 4-ClC6 H4 , 72%30c. R = 2, 4-Cl2C6H3 , 75%30d. R = 4-(CH3 )2NC6 H4 , 83%30e. R = 4-C2 H5 C6H4, 81%30f. R = 4-CH3 OC6H4 , 76%30g. R = 4-CH3C6H4, 80%30h. R = Naphthyl , 72%

Scheme 23.

P(O)(OEt)2

F

O

F

(EtO)2(O)P

THF

140 0C

F

P(O)(OEt)2

F

(EtO)2(O)P

P(O)(OEt)2

F

(HO)n

32 73% yield

Scheme 24.

O

RO

RORO

OMe

I

F

HP(O)(OEt)3

PDCl2, Et2N

85oC

O

RO

RORO

OMe

P

F

O

OROR

31-68% yield33

Scheme 25.

Treatment of a catalytic amount of DBU (20 mol%) witha mixture of diethyl 3-cyanoallylphosphonate 29 and N-tosylsulfonylimines gave diethyl 3-cyanobuta-1,3-dienylphosphonates 30 in 72-83% yields. All the products(30a-h) are assigned 1E,3Z configurations on the basis ofthe crystal structure of diethyl (1E ,3Z ) -3-cyano-4-naphthylbuta-1,3-dienylphosphonate 46h, the proton NMRspectra and the proposed reaction mechanism (Scheme 23)[40].

3.2. Fluorinated Vinylphosphonates

a) Diastereoselective synthesis of cyclic α -fluoromethyldienephosphonates, 32, using α -fluoroallenephosphonate, 31, as dienophile wasreported, (Scheme 24) [41]. The dimerization of α-fluoroallenephosphonate and its Diels-Alder reaction

with various dienes provide a diastereoselective routeto cyclic and bicyclic α-fluorovinylphosphonates, 32[42].

b) Gross et al. [43] reported the palladium-catalyzedstereoselective synthesis of (E)-and (Z)-α-fluorovinyl-phosphonates 33, which are analogs of glucose 6-phosphates (Scheme 25).

c) Fluorinated vinylphosphonates 34 were obtained inone-pot conversion of trifluoro ester to α-fluoro-β-trifluoro-β-alkoxy-vinylphosphonates (Scheme 26)[44].

3.3. Chlorinated Vinylphosphonates

New chlorovinylphosphonates 35 bearing a 1,3,2-dioxaphosphorinane ring which are useful for the


(R1O)2P(O)CFBr2

CF3

ORF

P

O

R1O

R1 O

(R1O)2P(O)CFSiMe3

CF3COOR

Me3SiCl

nBuLi

34

34a. R = iPr, R1 = Et, E/Z = 100:0, yield, 91%

34b. R = nBu, R1 = Et , E/Z = 100:0, 74%

34c. R = iBu, R1 = Et, E/Z = 100:0, 40%

34d. R =nBu, R1 = iPr, E/Z = 100:0, 67%

34e. R =nPr, R1 = iPr, E/Z = 100:0, 49%

34f. R = R1 = iPr, E/Z = 100:0, 32%

34g. R =nPr, R1 = Et, E/Z = 82:18, 76%

34h. R = Et, R1 = iPr, E/Z = 79:29, 58%

Scheme 26.

O

P

O

H

O OOHC

O

P

O O

OHO

SOCl2

O

P

O O

OO

S Cl

O

O

P

O O

OCl

- SOCl2

Toluene

35

Scheme 27.

R1

O

R2

P

HOR1

R2O

RO

RO

R1

P

R2

N3

ORO

RO

R1

P

R2

HO

ORO

RO

R1

P

R2

R3HN

ORO

RO

A1 A2 A3

A4A5

Scheme 28.

stereospecific synthesis of 5-chlorofurfuryl substitutedolefins and chloro-substituted dienes have been obtained byan easy, inexpensive route. The utility of some of these inthe synthesis of ferrocenyl- and anthracenyl-substitutedunsymmetrical acetylenes has been explored. The structuresof these vinylphosphonates was determined by the X-ray(Scheme 27) [45].

3.4. Amino-Vinylphosphonates

a) Synthesis of (3-amino-1-alkenyl)phosphonic acidsfrom allylic α- and γ-hydroxy-phosphonates has beenreported [46]. (3-azido-1-alkenyl)phsophonates A5was prepared regioselectivity by reaction of (1-hydroxy-2-alkenyl)phosphonates A2 and subsequent


O

NR

R

Et3NN

PH

Ph

RR

OOEt

OEt

A6

a. R = Me, yield, 38%b. R = Et, 37%c. R = (CH2)5 , ont isolated

+P(O)Cl3(EtO)2 POR1

R1 = H, Et

Scheme 29.

O

P

O O

H

R2

O

R1

CHO

O

P

O O

R

R1

O

O

P

O O

HO R

R1

O

Ac2O/Et3N

O1 a. R = R1 = Ph

b. R = R1 = 4-MePh

+

Scheme 30.

R1

P

OHR2

OMeO

MeO

Ac2 O

R1

P

OMeO

MeO

R2

OHR1

P

OMeO

MeOR2

O

NaOMe

R1 R2

OAc

P

OMeO

MeO

OP

R2

R1

O

MeO

+

O2

O3O4O5

Scheme 31.

thermal 1,3-rearrangement of the allylic γ-aminophosphonates A4 (Scheme 28).

b) The reaction of PhCH2C(O)NR2/P(O)Cl3 (R = alkyl)with diethyl or triethyl phosphite afforded E-vinylphosphonates A6 with high geometricalstereoselectivity and acceptable yields (Scheme 29)[47].

3.5. Oxo-Vinylphosphonates

a) Several oxo-phosphonates O1 were produced byoxidation of α -hydroxyphosphonates, which are

prepared by the Pudovik reaction of the cyclicphosphates (Scheme 30) [48].

b) Different vinylphosphonates, O2-O5, including 3-oxo-vinylphosphonates, O5, (Scheme 31), have beensynthesized in good yields by NaOCH3-catalyzedregioselective 1,2-addition of dimethyl phosphates toacyclic and cyclic α-enones at -35 oC [49].

c) Attolini et al. studied the reactions transformation ofcyclic dialkyl (3-oxo-1-cycloalkenyl) phosphonatesO 6 . Baker’s yeast-mediated enantioselectivereductions afford the corresponding dialkyl (3-


(n)

P

O OEtOEt

O(n)

P

HO

OOEt

OEt

(n)

P

OOEtOEt

HO

(n)

O

Baker's yeast

H2 O

30-38 0 C

*a. n = 1b = n=2c. n= 3

O6

O7

Scheme 32.

CH3

O

P(OEt)3P

O

OEt

OEtOEt

CH3

CH3

O

P

O

OEtOEt

Br

Br2

CH3

O

P

O

OEtOEt

NBS, CH2Cl2

- 5 0C,

99%

78%

heat99%

O8

O10

O9

Scheme 33.

P(O)(OR1)2

COOEt

S

S H

P(O)(OEt)2RCHO

R2S

R2S H

P(O)(OEt)2RCHO

S

S

P(O)(OEt)2

OH

R

R2S

R2 S

P(O)(OEt)2

OH

R

P(O)(OR1)2

HR2S

R2S

+ RSHAl-reagent

R = (CH2)3SH, R1 = OEt

R = (CH2)3SH, R1 = Ph

R = Et, R1 = Ph

S2

S2a. R1 = OEt, R2 = (CH2 )3S2b. R1 = OEt, R2 = (CH2)2

S2c. R1 = OEt, R2 = Et

S2d. R1 = Ph, R2 = (CH2 )3S2e. R1 = Ph R2 = (CH2)2

R = tBuR = iPrR = cyclohexylR = Ph

S3

S4

R = tBuR = iPrR = cyclohexylR = Ph

Scheme 34.

hydroxy-1-cycloalkenyl) phosphonates O7, (Scheme32) [48,50].

d) 2,2,2-Triethoxy-oxaphospholene O8 reacts undermild, neutral conditions with bromine to produced 3-oxo-vinylphosphonate O10 in high yields (Scheme33) [51].

3.6. Thio-Vinylphosphonates

Phosphonoketene dithiocetals, (S2a-e) were obtained ingood yields by the reaction of ethyl phosphonoacetates withthiols in the presence of an alkylaluminium dichloride ordialkylaluminium chloride (Scheme 34) [52]. Reaction of2,2-dithio-1-phosphovinyl phosphonates with aldehydes


PR

OOEt

OEt

BO

O

HB

PR

H

OOEtOEt

O

O+

B1

Scheme 35.

P

OEtO

EtO

R2 P

R1

R

OOEt

OEt

(CH2)3COKDMSO

R1

R

P

OOEt

OEt

PO

OEtEtO

P

O

OEtOEt

P

O

OEtEtO

R = R1 = (CH2)5

54%

R = H, R1 = CH2 Ph

91%

R1 = (CH2)5CH3

R = H

98 %

R = H

R1 = CH(CH3 )2

36

K1e

K1d K1b

K1aK1c

Scheme 36.

afford 1-(hydroxymethyl)thiovinylphosphonates S3, S4 ingood to moderate yields.

3.7. Boranated Vinylphosphonates

Hydroboration of alkynylphosphonates with pinacolboraneproceeds to give phosphonoboronates B1 (Scheme 35).Surprisingly, such compounds have not been reported before[53].

4. REACTIONS, ISOMERIZATIONS ANDTRANSFORMATIONS OF VINYLPHOSPHONATES

4.1. Allylic Phosphonates from Vinylphosphonates

A facile route to allylic phosphonates via base-catalyzedisomerization of the corresponding vinyl phosphonates K1a-e has been reported (Scheme 36) [54].

4.2. Epoxides from Vinylphosphonates

Epoxyalkylphosphonates are useful intermediates in thesynthesis of modified natural and synthetic polymers [55],and also in the preparation of bioactive substances [56].

A new stereoselective route to substituted 1,2-epoxyalkylphosphonates through oxidation of correspondingalk-1-enylphosphonates, K 2 , by ‘in situ’ generatedethylmethyldioxirane has been described (Scheme 37) [57].

P

R3R2

R1

OOEt

OEtO O

EtMe P

R3R2

R1

O

OEt

OEt

O

+

R1 = alkyl, Ph

R1 = alkyl, Ph, H

R1 = alkyl, H

K237

Scheme 37.

4 .3 . Hydroxy(methyl) Phosphonates fromVinylphosphonates

Diethyl trans-1,2-epoxyphosphonates were synthesizedstarting from the corresponding diethyl t r a n s -vinylphosphonates 38 by the previously described reaction


RPO3H2

H

H

R

R

OH

PO3H2

H

OH

PO3H2

H

H

OH

R

R

OH

PO3 H2

H

OH

PO3 H2

H

H

OH

R

R

OH

PO3H2

H

H

OH

H

PO3 H2

H

H

OH

+

55

Aspergillusniger

K3 K3'

97:3 dioxane/water

K4a

K4bK4c

K4d

erythro (1S, 2S)

erythro (1S, 2R)threo (1R, 2S)

threo (1R, 2R)

R = H, yield 81%, threo:erythro 64:36R = p-Me, 79%, 85:15R = o-Me, 66%, 79:21R = m-Me, 72%, 70:30R = p-Br, 23%, 60:40R = p-Cl, 73%, 63:37

Scheme 38.

with dioxirane [58]. Compounds 38 were prepared bystandard Wittig–Horner reaction of tetraethylmethylenebisphosphonate with aromatic aldehydes inaqueous two-phase system [59]. The threo isomers K3a-dwere synthesized independently by the Sharp less approach,using AD-mixes as catalysts for the dihydroxylation of thecorresponding trans-vinylphosphonates 38. The use of AD-mix-β gave preferentially the (1S,2S) isomer. Consequently,the use of AD-mix-α resulted in the preferential formation ofthe isomer (1R,2R). Quinine have been used as a chiralselector to determine the course of biocatalytic hydrolysis oftrans-epoxyethanephosphonates by the action of Aspergillusniger and thus verify the usefulness of method for theevaluation of the stereospecifity of this process. Contrary tothe chemical hydrolysis, biocatalysis gave preferentiallyerythro-1,2-dihydroxyl-akanephosphonates (with only traceamounts of the threo isomers), which were obtained in goodyields and with enantioselectivities strongly dependent onthe structure of the substrate used. At this moment we are,however, unable to determine, which of the two formedisomers (1S,2R) or (1R,2S) is the major one (Scheme 38)[60].

4.4. Alkynyl Vinylphosphonates from Vinylphosphon-ates

The β-hetero-substituted vinylphosphonates 39a-c ontreatment with LDA or LTMP were readily lithiated at theα -position of the phosphono group, and the resulting α -lithiovinylphosphonates were trapped with variouselectrophiles to afford the corresponding α-functionalizedvinylphosphonates 40 in 55-96%yields. The Friedel-Craftsreaction of α -(silyl)- or α -(germyl)-phosphonoketenedithioacetals, the reaction with acid chlorides gave α -acylated phosphonoketene dithioacetals, 41 in 53-91%yields. The palladium-catalyzed cross-coupling reaction of β-ethoxy-α-(tributylstannyl) vinylphosphonate with a varietyof organic halides (R = acyl, allyl, aryl, etc.) provided β-ethoxy-α -substituted vinylphosphonates in good tomoderate yields. The palladium-mediated cross-couplingreaction of α -(iodo)vinylphosphonates with terminalacetylenes afforded α-alkynylated vinylphosphonates K5 in69-83%yields. Several α-functionalized β-hetero-substitutedvinylphosphonates were applied to the synthesis of pyrazolesand an isoxazole possessing a phosphono function (Scheme39) [61].


P

HR1

R2

OOEtOEt

P

ER1

R2

OOEtOEt

P

R1

R2

OOEtOEt

R

P

CORR1

R2

OOEtOEt

39 40 41

K5

R1 = OEt, R2 = H, E = SiMe3, GeMe3, SnBu3

R1 = R2 = SEt, E = SMe, Br, I

Scheme 39.

4.5. Suzuki Coupling of Boranated Vinylphosphonates

Hydroboration/Suzuki coupling of alkenylphosphonates,B1, with PBH, in a one-pot procedure to yield trisubstitutedvinylphosphonates 42 , 43 in good overall yields andprovides a new synthesis of these compounds (Scheme 40)[53].

P

BH

R

OOEtOEt

O

O

P

HB

R

OOEtOEt

O

O

P

HAr

R

OOEtOEt

P

ArH

R

OOEtOEt

ArIPdLn PdLn

ArIPdLn

B1

B242

43

Scheme 40.

4.6. Cycloadducts Formation

Vinyl phosphonates 44 α-substituted with carboxylate,nitrile, sulfone and phosphonate groups reacted with N-buta-1,3-dienylsuccinimide to give [4 + 2] ortho-cycloadducts as

mixtures of endo/exo stereoisomers K6, K7 (Scheme 41)[62].

NOO

65 0C

YX

CH3CN

NOO

H X

Y

NOO

H X

Y

+

44

K6a (endo or cis) K7b (exo or trans)

X = P(O)(OMe)2, Y = COOMe, yield, 95% a:b, 65:35X = P(O)(OEt)2, Y = COOMe, 93% a:b, 55:45X = P(O)(OEt)2, Y = CN, 80% a:b, 46:54X = P(O)(OEt)2, Y = COOEt, 93% a:b, 55:45X = P(O)(OEt)2, Y = SOOMe, 42% a:b, 52:48X = P(O)(OEt)2, Y = P(O)(OEt)2, 10% X = P(O)(OEt)2, Y = H, no reaction

Scheme 41.

4.7. Dienes Formation from Vinylphosphonates

Transition metal-catalyzed arylation and alkenylation of theα -bromovinylphosphonates 45 were investigated withorganoboranes and borates. Arylation was successful withthe aryl boronic acids and a palladium catalyst, to produceK8, while alkenylation was found to proceed with alkenylborates and a nickel catalyst to afford the diene product K9(Scheme 42) [63].


P Br

R1

O

EtO

EtO

ArB(OH)2

C5H11

B

O

OMe

Li+

P Ar

R1

O

EtO

EtO

C5H11

Me

PO

EtO OEt

45 E, Z-isomers

+-

Ni cat

THF, 3h

K8

K9 2E-isomer, 59% 2Z-isomer, 19%

Scheme 42.

4.8. Diels-Alder Reaction of Vinylphosphonates

The Diels-Adler reactions between diethyl 3-oxo-vinylphosphonate, 46 and cyclopentadiene and furanproduced the corresponding diastereomers, K10-K 1 3(Scheme 43) [64].

O

O

P

O

OEtOEt

O

P

COCH3

OOEt

OEt

O

COCH3

PO OEt

OEt

P

COCH3

OOEt

OEt

O

COCH3

PO OEt

OEt

++

46

K10

K11

K12

K13

Scheme 43.

Asymmetric synthesis of β-and γ-amidophosphonates,K14 and K15 by Diels–Alder reaction between thevinylphosphonate 46, 47 and chiral aminodiene was reported(Scheme 44) [65].

(MeO)2(O)P

MeOOC

NO

Oi-Pr

O

O

P(O)(OEt)2

NO

Oi-Pr

O

NO

Oi-Pr

O

O

P(O)(OMe)2

NO

Oi-Pr

O

P(O)(OMe)2

COOMe

+

92%

+

47

46

K14

K15

Scheme 44.

REFERENCES[1] (a) Hartly, R. In The Chemistry of Organophosphorus Compounds

1996, John wiley & sons, New York, USA. (b) Corbridg, D. InPhosphorus 1990, Fourth Edition, Elsevier, New York, USA.

[2] (a) Harnden, R.; Parkin, A.; Parratt, J.; Perkin, R. J. Med. Chem.1993, 36, 1343. (b) Smeyers, Y.; Sanchez, F.; Laguna, A.; Ibanez,N.; Ruano, E.; Perez, S. J. Pharm. Sci. 1987, 76, 753. (c) Megati,


S.; Phadtare, S.; Zemlicka, J. J.Org. Chem. 1992, 57, 2320. (d)Lazrek, H.; Rochdi, A.; Khaider, H.; Barascut, J.; Imbach, J.;Balzarini, J.; Witvrouw, M.; Pannecouque, C.; De Clerq, E.Tetrahedron 1998, 54, 3807. (e) Smith, P.; Chamiec, A.; Chung,G.; Cobley, K.; Duncan, K.; Howes, P.; Whittington, A.; Wood, M.J. Antibiot. Tokyo 1995, 4 8, 73. (f) Holstein, S.; Cermak, D.;Wiemer, D.; Lewis, K.; Hohl, R. Bioorg. Med.Chem. 1998, 6, 687.(g) Chance, L.; Moreau, J. US Patent 3910886, 1975.

[3] (a) Jin, J.; Hua, J. US Patent 3925506, 1975. (b) Fujimatsu, M.;Miura, M. Japanese Patent 86-250155; Chem. Abstr. 110, 9644k.

[4] (a) Spak, A.; Yu, A. US Patent 4088710, 1978. (b) Fuller, B.; Ellis,W.; Rowell, R. US Patent 5683820, 1997.

[5] (a) Shukla, J. US Patent 4241125, 1980. (b) Welch, C; Gonzalez,E; Guthrie, J. J. Org. Chem. 1961, 26, 3270.

[6] For a review: (a) Minami, T.; Motoyoshiya, J. Synthesis 1992, 333.(b) Thomas, A.; Sharpless, K. J. Org. Chem. 1999, 64, 8379. (c)Lee, S.; Lee, B.; Lee, C.; Oh, D. Synth. Commun. 1999, 29, 3621.(d) Telan, L.; Poon, C.; Evans, S. J. org. Chem. 1996, 61, 7455. (e)Zhao, Y.; Pei, C.; Wong, Z.; Xi, S. Phosphor Sulfur Silicon 1992,66, 115. (f) Kim, D.; Rhie, D. Tetrahedron 1997, 53, 13603. (g)Nagaoka, Y.; Tomioka, K. J. Org. Chem. 1998, 63, 6428. (h)Defacqz, N; Touillaux, R.; Marchand-Brynaert, J. J. Chem. Res.-S 1998, 512.

[7] For a complete list, see the IBM patent data base a t :www.delphion.com.

[8] Normant, J. F. Synthesis 1972, 63. (b) Posner, G.H. Org.React.1972, 19, 1. (c) Jukes, A.E. Adv. Organomet. Chem. 1975, 12,215. (d) Posner, G.H. Org. React. 1978, 22, 253. (e) Normant,J.F.; Alexakis, A. Synthesis 1981, 841.

[9] (a) Corey, E.J.; Katzenellenbogen, J.A. J. Am. Chem. Soc. 1969,91, 1851. (b) Siddall, J.B.; Biskup, M.; Fried, J.H. Ibid. 1969, 91,1853. (c) Klein, J.; Turkel, R.M. Ibid. 1969, 91, 6189. (d) Klein, J.;Aminadav, N.J. Chem. Soc.C 1970, 1380.

[10] (a) Vermeer, P.; Meijer, J.; Eylander, C. Recl. Trav. Chim. Pays-Bas 1974, 93, 240. (b) Truce, W.E.; Lusch, M.J. J. Org. Chem.1974, 39, 3174. (c) Truce, W.E.; Lusch, M.J. Ibid. 1978, 43, 2252.(d) Fiandanese, V.; Marchese, G.; Naso, F. Tetrahedron Lett.1978, 5131. (e) Meijer, J.; Vermeer, P. Recl.Trav.Chim.Pays-Bas1975, 94, 14.

[11] Aguiar, A.M.; Smiley Irelan, J.R .; J. Org. Chem. 1969, 34, 4030.[12] Axehad, G.; Laosooksathit, S.; Engel, R.; J. Org. Chem. 1981, 46,

5200-5204.[13] Gil, J.M.; Oh, D.Y. J. Org. Chem. 1999, 64, 2950-2953.[14] Cristau, H.J.; Xavier Y.; Mbianda, Y.; Beziat, M.B. J. Organomet.

Chem. 1997, 52, 301-311.[15] Quntar, A.A.; Dembitsky, V.M.; Srebnik, M. Org. Lett. 2003, 5,

357-359.[16] Quntar, A.; Srebnik, M. Chem. Comm. 2003, 59, 58.[17] (a) Lipshutz, B.J.; Bhandari, A.; Lindsley, C.; Keil, R.; Wood,

M.R. Pure & Appl. Chem. 1994, 66, 1493. (b) Lipshutz, B.H.; Ace.Chem. Res. 1997, 30, 277.

[18] Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.[19] (a) Negishi, E.; Cederbaum, F.K.; Takahashi, T. Tetrahedron Lett.

1986, 27, 2829. (b) Buchwald, S.L.; Nielson, R.B.; Chem. Rev.1988, 88, 1047. (D) Larock, R.C.; In Comprehensive OrganicTransformations; VCH Publishers; New York, 1989. (c) Negishi,E. Chemica Scripta 1989, 29, 457. (d) Hanzawa, Y.; Ito, H.;Taguchi, T. Synlett. 1995, 299.

[20] Quntar, A.; Srebnik, M. Organic Lett. 2001, 3, 1379.[21] Quntar, A.A.; Srebnik, M. J. Org. Chem. 2001, 66, 6650-6653.[22] Quntar, A.; Melman, A.; Srebnik, M. Synlett 2002, 1, 61.[23] Kouno, R.; Tsubota, T.; Okauchi, T.; Minami, T. J. Org. Chem.

2000, 65, 4326- 4332.[24] Nagaoka, Y.; Tomioka, K. J. Org. Chem. 1998, 63, 6428-6429.[25] Hammersvchmitdt, F.; Zbiral, E. Liebigs Ann. 1979, 492-502.[26] Brunner, H.; Le Cousturier, N.; Pierre J. Synlett 2000, 201-204.[27] (a) Mohamed-Hachi, A.; About-Jaudet, E.; Combret, J.; Collignon,

N. Synthesis 1997, 653-655. (b) Degenhard C.; Burdsall C. J. Org.Chem. 1986, 51, 3488.

[28] Degenhard, C.; Burdsall, C. J. Org. Chem. 1986, 51, 3488.

[29] Jiao, X.; Bentrude, W. J. Amer. Chem. Soc. 1999, 121, 6088-6089.[30] Attolini, M.; Maffei, M.; Principato, B.; Pfeiffer, G. Synlett. 1997,

384-386.[31] Lu, X.; Tao, X.; Zhu, J.; Sun, X.; Xu, J. Synthesis 1989, 848.[32] Zhao, Q.; Han, L.-B.; Goto, M.; Tanaka, M. Angew. Chem., Int.

Ed., 2001, 40, 1929.[33] Han, L.B.; Tanaka, M. J. Am. Chem. Soc. 1996, 118, 1571.[34] Ogawa, T.; Usuki, N.; Ono, N. J. Chem. Soc., Perkin Trans. 1998,

1, 2953.[35] (a) Kazankova, M.A.; Trostyanskaya, I.G.; Lutsenko, S.V.;

Efimova, I.V.; Beletskaya, I.P.; Russ. J. Org.Chem., 1999, 35, 428.(b) Kazankova, M.A.; Trostyanskaya, I.G.; Lutsenko, S.V.;Beletskaya, I.P. Tetrahedron Lett., 1999, 40, 569.

[36] Trostyanskaya, I.G.; Titskii, D.Yu.; Anufrieva, E.A.; Borisenko,A.A.; Kazankova, M.A.; Beletskaya, I.P. Izv. Ross. Akad. Nauk,Ser. Khim., 2001, 2003.

[37] Hirao, T.; Masunaga, T.; Ohshiro, Y.; Agawa, T. TetrahedronLett.,1980, 21, 3595.

[38] (a) German Offen. no.2 118 223; Chem.Abstr., 1972, vol.76, no.34399w. (b) Honig, M.L.; Martin, D.J. Phosphorus 1974, 4, 63.

[39] Afarinkia, K.; Evans, M.; Jocelyn, C.; Bueno, J. Tetrahedron Lett.1998, 39, 433- 434.

[40] (a) Shen, Y.; Jiang, G.F.; Sun, J.; J. Chem. Soc., Perkin Trans.1,1999, 3495–3498. (b) Yonghong, G.; Takuo, H.; Haimnond, G.Chem. Commun. 2000, 395-396.

[41] Classen, R.; Hagele, G. Fluorine Chem. 1996, 77, 71-81.[42] Yonghong, G.; Takuo, H.; Haimnond, G. Chem. Commun. 2000,

395-396.[43] Gross, R.S.; Mehdi, S.; McCarthy, J.R. Tetrahedron Lett. 1993, 34,

7197.[44] Shen, Y.; Zhang, Y. J. Fluorine Chem. 2001, 108, 69-71.[45] Muthiah, C.; Praveen Kumar, K.; Aruna Mani, C.; Kumara

Swamy, K.C. J. Org. Chem. 2000, 65, 3733-3737.[46] Öhler, E.; Kotzinger, S. Liebigs Ann. Chem. 1993, 269-280.[47] Wang, W.; Xu, G.; Cao, R.; Liu, L. Heteroatom Chemistry 2000,

11, 512-517.[48] Kumaraswamy, S.; Senthamizh, R.; Swamy, K. Synthesis 1997,

207-212.[49] Öhler, E.; Zbiral, E. Chem. Ber. 1991, 124, 175-184.[50] Attolini, M.; Bouguir, F.; Iacazio, G.; Peiffer, G.; Maffei, M.

Tetrahedron 2001, 57, 537-543.[51] McClure, C.; Grote, C.W. Tetrahedron Lett. 1991, 32, 5313-5316.[52] Minami, T.; Okauchi, T.; Matsuki, H.; Nakamura, M.; Ichikawa,

J.; Ishida, M. J. Org. Chem. 1996, 61, 8132-8140.[53] Pergament, I.; Srebnik, M. Org. Lett. 2001, 3, 217-219.[54] Kiddle, J.J.; Babler, J.H. J. Org. Chem. 1993, 58, 3512-3574.[55] Beck, H.N.; Mac Williams, D.C.; (Dow Chemical Co.); US Pat. 4,

692,355; Chem. Abs.107 238808x.[56] (a) Courregelongue, J.; Frehel, D.; Maffrand, J.P.; Paul, R.; Rico,

I. Fr.Pat. 2, 596, 393, Chem.Abs. 108, 94780c. (b) Hendlin, D.;Stapley, E.; Jackson, M. Sciences 1969, 166, 122. (c) Christensen,B.G.; Leanza, W.J.; Beattie, T.R. Sciences 1969, 166, 123.

[57] Cristau, H.K.; Mbianda, X.Y.; Geze, A.; Beziat, Y.; Marie-Benedicte, G. J. Organometallic Chem. 1998, 57, 189–193.

[58] Cristau, H.J.; Yangkou-Mbianda, X.; Gaze, A.; Beziat, Y.; Gasc,M.B.J. Organomet. Chem. 1998, 57, 189–193.

[59] Mikolajczyk, M.; Grzejszczak, S.; Midura, W.; Zatorski, A.Synthesis 1976, 396– 398.

[60] Maly, A.; Lejczak, B.; Kafarski, P. Tetrahedron Asymmetry 2003,14, 1019–1024.

[61] Kouno, R.; Okauchi, T.; Nakamura, M.; Ichikawa, J.; Minami. T.J. Org. Chem. 1998, 63, 6239-6246.

[62] Defacqz, N.; Touillaux, R.; Marchand-Brynaert, J. J. Chem. Res.(S), 1998, 512-513.

[63] Kobayashi, Y.; William, A.D. Org. Lett. 2002, 4, 4241.[64] McClure, C.K.; Hansen, K.B. Tetrahedron Lett. 1996, 37, 2149-

2152.[65] Robiette, R.; Marchand-Brynaert, J. J. Chem. Soc., Perkin Trans.

2, 2001, 2155-2158.

Received: 1 February, 2004 Accepted: 4 March, 2004

Recent Synthesis and Transformation of Vinylphosphonates

Documents

Transcript of Recent Synthesis and Transformation of Vinylphosphonates