Chapter 2 Application of Diels-Alder Cycloaddition Chemistry for

Heterocyclic Synthesis

ALBERT PADWA Emory University, Atlanta, GA, USA

2.1

INTRODUCTION

The importance of the Diels-Alder reaction in organic synthesis derives in large part from its ability to generate six-membered rings containing several contiguous stereogenic centers in one synthetic operation. In recent years the Diels-Alder reaction of heterosubstituted 1,3-dienes and dienophiles has emerged as a powerful method for preparing highly functionalized heterocyclic ring systems. The aim of this chapter is to provide an indication of the wide assortment of Diels-Alder chemistry that has been used for heterocyclic synthesis. Although some older references are mentioned, the coverage has been selected from the last fifteen years, including new applications and modifications of older reactions and innovations. The organization of the review is according to structural type and represents an extension of an approach used earlier in Volume 6 of PHC. Each synthetic sequence is accompanied by references to the original literature. We hope that you find this unusual format to be useful. The following reaction sequences provide a sampling of some noteworthy transformations in this area of heterocyclic chemistry.

2.2

Reaction Schemes
I Imino Die/s-Aider Reactions I
Reviews: Boger [87M1001] Weinreb [82TET3087, 79HET949]

Imines as Dienophiles [81TL4607]

1) benzene OMe/ A, 15 h O O Ph3P=NCO 2tBu NCO2tBu ]~ 2) H3 O+ ,,J~N/~I H~ " "COOEt '~ HjjI-,COOEt + J ' ~ 84 % ;. tBuO OSIMe3 EtO2C O
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Lewis Acid Catalyzed Reactions of Imines

Danishefsky [82TL3739]

OMe ,~~ Me3SiO +

H- y

'NCH2Ph ' U. ~.

1.0 eq ZnCI2,THF rt, 36-38h 69 %

~ O

IP

21

22

Application of Diels-Alder Cycloaddition Chemistry

Danishefsky - Application of the aldimine diene-cyclocondensation reaction for total synthesis [86JOC3915] H EtOyOSiEt3 ~ ./',~C02Me

IJ, ,

+
OMe

50 %

ZnCI2

N
OMe

Holmes- Synthesis of piperidine alkaloids using a tosyl imine [87TL813] 0 HyCO2Me ~]1OSiMe3 Lewisacid Tos~N + 1) MeCO3H. I" OH OH ~ 2) LiAIH4 H3 O+ " TosN CO2Me

Grieco - Diels-Alder reaction of iminium salts generated under Mannich conditions in aqueous solution [85JACS1768] 1.3 eq PhCH2NH2-HCI 1.3 eq HCHO H2O, 55 ~ 96 h 62 % ~N CH2Ph

~-

1.3 eq PhCH2NH2-HCI 1.3 eq HCHO rt, 23 h 45 %

I.,,

t ~

N CH2Ph

A chiral amine as an imino precursor

O
+

Me~,,,,H
H2Nq "Ph

HCHO/H20 86 % =

ON

Ph

Me_ H

9 1

Grieco- Cyclocondensation of C-acyl iminium ions with cyclopentadiene [86TL1975] O + Me-NH2 HCI O

H20, rt, 22 h
82 %

Me 4.2 9 1

Application of Diels-Alder Cycloaddition Chemistry

Grieco - Iminium ions derived from aryl amines and aldehydes function as heterodienes [88TL5855] i~ + NH2" TFA 5equiv H20 MeCN rt, l h 98%

23

= H H

+ H 3.7 ' 1 H

Grieco - Intramolecular imino Diels-Alder reaction [85JACS1768, 86JOC3553]

NH3CI"

HCHO/H20
, v

50 ~ 48 h
95 %

"H

CI

CHO

PhCH2NH2, HCI EtOH-H20 70 ~ 63 %

H,,, N H h 2.5 ' 1

H sa e

NH
h

"~CHO

MeNH2 HCI
H20/EtOH (1" 1) 70 ~ 66 %

MeN
Dihydrocannivonine

Vollhardt - Oxime ethers as dienophiles [80JACS5245]

CpCo(CO)2 SiMe3 ~ N,,OMe 45 %

O H Me3Si~.~~

MeaSi~

N'OMe

Me3Si ~..,"L~..,'~",~ N,,OMe

24

Application of Diels-Alder Cycloaddition Chemistry

Boger- Vinyl sulfonylimines as azadienes - preparation from the corresponding oximes or unsaturated aldehydes [91JACS1713] OH| M S(O)Ph 25~ S02Ph

Mean

PhSOCI.
-20tO 0 ~

SO2Ph
I

H.~O Ph

PhSO2NH2MgS04

H~ Ph

Reaction with electron-rich dienophiles

$O2Ph I N~,,.Ph + CH2 100 ~ dioxane 89 %

SO2Ph i EtO,~" i -Ph

o

OCH2Ph CH2CI2 12 kbar

28% ~

OCH2Ph

H" Me

L,j

"Me

SO2Ph +

H,,,~OMe C II CH2

CH2CI2 12 kbar 54 %

I =

OMe CH2

Application of Diels-Alder Cycloaddition Chemistry

25

Weinreb - Intramolecular Die/s-Aider reactions of N-acyl azadienes [85ACR16, 79JACS5073, 81JACS6387, 82JACS7065]

c~
O

650~ ll~s
-HOAc

CH2~,~ I~/N~ O

= 73'0

~N~ O

,c o-- ,co
73 % ~ O 1) H2,Pd 2) B2H8

"~176I Q

6-Coniceine
Weinreb - Acylimines as key intermediates for alkaloid synthesis [83JOC3661]

OBn
o-dichloro- --N H /~ benzene .--i./

,,OBn ~__~._.~ OBn

o//-"
.~ =

,,OH
epi-Lupinine

r'~Y
AcO O

178~

930/.
O

Rigby - [4+2]-Cycloadditions of vinyl isocyanates [84JOC4569, 86JOC1374, 89JOC224, 89JOC4019, 89JOC5852, 89SC2699, 91JACS8975]

[~ ~C~ 0 0

H2/ Pd (C) 73 %

MeO MeO" ~

NCO

~ + ~ 34 % =-

OMe

MeO
MeO" ~
I

v OMe

26

Application of Diels-Alder Cycloaddition Chemistry

4+2-Cycloaddition reaction of vinyl isocyanates with benzyne

58%
!

NCO

NH2
good synthon for ben~ne

Magnus - Indole 2,3-quinodimethane strategy for synthesis of indole alkaloids [84ACR35] 1'~ ~:~/'~ E"N NI~CH2
R SiMe3

E+

J R

CH2 O

N
R

N
L~

,3,00

~ ~ , ,H,,..~,,,J ~
"''~Et R I(+)- Aspidospermidine ]
I

I.L IJ.. CH2 C'3CCH20COC' ~"~"/"~Nf'Me 46 % I R

N~ S P h

O O 33"---~/0

PhS~ N I R
O

f
""Et

R
I Acvlationl
o

CH2

,Cl1-C12 ]-........~,, bond L,= ~1~,, .''~?E'

" ~ "N R
. . . . . . . . . . . . . . . . . . . . . .

~~

"=

"
~L~~'N ~'~'~'"Et R

Kopsanone and Tabersonine

Me ~,,.~ CycllzationlI
~ . . . . . . . . . . . . . . . . . . . . . . .

~ . . . . . . . . . . . . . . . .

~N'~
R
I

Ne~ jJl M CI

c,~oCH~OCOC," ~,
PhCI

i-PrNEt,120~

~ ' ~ N J I~ " C I
R

~~'"~

E"N"~'I H,,.

Application of Diels-Alder Cycloaddition Chemistry

Die/s-Aider reactions with inverse electron demand Bradsher -Azonia polycyclic aromatic compounds as dienes [55JACS4812,

27

58JACS933, 68JOC390, 73CC156] 2R~R 1

Br" +

R ..R1
R2.~H

heat = 66-100 %

(~+N~~

Br-

mixture of stereoisomers C104" r ~ + N H EtQ ~..... H -- +'~20Et ~'~N+.~~

CH2=C(OEt)2 .= 25 ~ 1 h 89 %

C104"

Regioselective-- ethoxygroups are nonadjacentto quaternarynitrogen

Cycloaddition of isoquinolinium salts Franck- Use of vinyl sulfides for synthesis of 1-naphthaldehydes [89JOC1097]

,~ts
R' RtR~ ./~--" H

R 1 = R2= H

.~r R1

1)H+, H20
2) K2CO3, MeOH, H20

CHO

overall 91%
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . o

Kahn.- Oxidative intramolecular cycloaddition of an azodicarbonyl system [88JACS1638]

NHBn COC'

O
O O
exo-adduct

28

Application of Diels-Alder Cycloaddition Chemistry

80JACS3632, 85JACS5534]
t-BuMe2SiO,,

Die/s-Aider reaction of nitroso compounds [84JOC4741, 86JACS1306,78TL4767,

N r

jT"OMe CsF MecN" 20 oC

~ r OMe

83%
_ ,,0..,,,OMe _,,0,..,OMe

Note: dihydroxazinering adopts a boat-like conformation to take advantage of anomeric effect

70" 13 Kibayashi- Stereospecific total synthesis of GTX 223AB [86TL5513] Pr4N104= CHCI3 O H 1) Zn, HOAc 2) BnOCOCI Na2CO3/CHCI3 MsCI, Et3N 31H2,Pd/C,MeOH
I=, 4" -"

~
several steps

Gephyyrotoxin 223AB

Weinreb - Intramolecular N-sulfinyl carbamate cycloaddition [84JOC3243, 85TET1173]

S" Me~l~ OH

,.~o .oc,,; .-~~ ] "~176 o,,.~o

P"CH'~176 O~h L~

pyridine

0 .,~.x. R

N"~O "-"'~ =H~

co~oonon, o, aminoglycoside antibiotic 66.40-D

Application of Diels-Alder Cycloaddition Chemistry

Weinreb - Use of N-sulfinyl cycloadducts for synthesis of homoallylic amines [83TL987, 84JACS7861, 84JOC3243, 85TET1173] Me Me Me O" Me. / O Mev'L~4/' 1)NaOH Me,,~,,~l~leS; -SO2 TosN=S=O= . ~ , Me~H. ~ 85%= Me PhMe,0 ~ NTos 2) HaO ,= Me ."" NHTos overall Me Me H Me

29

Me NHTos "_- Me Me

Weinreb - N-Sulfinyl compounds as heterodienophiles [84JACS7861, 84JOC3243, 85TET1173]

.o,
~.

o NH2

SOCI2 pyridine"
"15~

N 85 %
r

1) PhMgBr 2) (MeO)3P 85 % n-C13H27

13H27

'~n .C13(~27

n-C13H27~ ~ O "
i

Ba(OH)2
Ii=

_NH2 n-C13H27~ O H
threo-Sphingosin

OH

O H

E.threo .carbamate

Weinreb - Stereochemica/contro/[84JACS7867] Me +
Me

Me

.oS" II NCO2Bn

PhMe 25 oC95 %

I[~ ~
Me

,oCO2Bn

PhMgBr

H.,,,I~::~ Me 2,3-eigmatropic
Me,~Ix. " "OSPh H NHCO2Bn

Me + . = "1 ~s "r" /

P(OMe)3 85 %

OH NHCO2B n
threo.hydroxy carbamate

MeOH = Mei~~,,,~Me

Me'~NI~I~O2Bn ]

Note: Only E-isomerdue to reversible [2,3]-sigmatropic rearrangement

30

Application of Diels-Alder Cycloaddition Chemistry

Weinreb -

Diels-Alder adducts of sulfur dioxide bis(imides)

Me Me

[84JACS7867]

S ~'NR II NR

benzene "' 25 oc

i RN

I Me

1) PhMgBr
=

2) P(OMe)3
83-92 %

Me

NHR .,,~ .,~ . Me NHR

Me R = Tos, C02Me

PhMgBr Me
2,3-

T P(OMe)3 Me shift H'~i~-Sp h I-I" "NHR

Intermolecular [4+2]-Cycloadditions employing a-pyrones as dienes

Moody

3-Pyridyne as a dienophile

[88JCS(P1)247]

NH2,,v,,,% N HO2C i ~ / ,

1) HNO2 2) Me2NH

Me2N_N=N~

M6

72%-

H02C ] ~ ~ ''
M6

Me E//ipticine MeCN A
+

Me BF3-Et20 T Ac20 44 %

Me

OH

Me

Me Isoellipticine 40 % (1 91)

KOH, &

N" H

Application of Diels-Alder Cycloaddition Chemistry

Boger [84JOC4045] r MeO Me 2.2 eq Nail, THF

31

MeO2C -

H "C=C(C02Me)2 ~,'
81% MeO2C MeO Me
.OMe 7 steps

7 steps from 4-benzyloxycyclohexanone

10 eq H2C=C(OMe)2
toluene,140 ~ 21 h

~OH
.,, MeO 17%
Me

Me

75 % MeO
Me

Juncusol

Intramolecular 4+2-Cycloadditions of a-pyrones

Martin - Azatriene gives hydroisoquinoline [85JACS4072] BN n ~0
an N

xylene ID reflux
93 %
H

~l o

RO

RO
OMe

(:/:)-Reserpine Hetero Die/s-Aider Reactions Reviews: Boger and Weinreb [87MI001, 91MI402, 91MI451] Intramolecular Cycloadditions Involving Oxabutadienes Tietze -in situ generation of heterodiene via Knoevenagel condensation
[87ACIE 1295, 82ACIE221]
o

~CHO

0_.~ O ~
OMe + ~ , . 0
I I

"T

o ~ o ~ io~~.~ o
.
exo.E-anti

(S)-Citronellal
preferential 5,6-cis-fused cycloadduct from endo. E-syn transition state = 52 %

L ~176
endo-E-syn

0~.,,.0,~ H

H .C02Me
6 steps

~,~ 0
O

Osugar

i-de 9 98 %

Deoxyloganin

32

Application of Diels-Alder Cycloaddition Chemistry

Tietze - Asymmetric induction effected by remote stereogenic center[82ACIE221] O

+

O DMF
w

O (R)-Citronellal R=
C5Hll

100 ~

preferential 6,6-trans-fused cycloadduct 65 %

1) LDA, PhSeCI 2) mCPBA -40 ~ to rt

w

R
i-de 9 98 %

46 % R

(-)-(9R)-Hexahydrocannabinol

Talley o-Quinone methide cycloaddition controlled by remote chiral center [85JOC1695]

HO CF3CO2H CHCI3 OH Me 87 %

Danishefsky- Lanthanide catalysis [84TL721]

~CHO 0.05 eq Yb(fod)3,. rt, 80 h ~ 80 % EtO~/u~"

EtO~l
==~CHO 0.05 eq Yb(fod)3, rt, 80 h 60-80 %

endo product only

EIO mixture endo + exo

Application of Diels-Alder Cycloaddition Chemistry

33

I"`'`r~176

I
RIJR1 + hv = R R1

Thioketones are generally readily available to undergo thermal or photochemical cycloadditions

Vedejs - Unstable thioaldehydes can be generated and trapped in situ by a photochemical method[80JOC2601, 83JACS6999, 82JACS1445, 83JACS1683, 86JOC1556, 88JOC2226, 88JACS5452]

o ~~

h~

[ o

..~

C
~ Y
H

Vedejs - Intramolecularthioaldehyde cycloaddition shows only moderate stereoselectivity [88JOC2220]

hv

phi

"

0
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

12" 1)

Vedejs - Trapping of thioaldehyde by both Die/s-Aiderand ene reactions [88JOC2220]

c.O2Et

Ph.~ O

O O

hv =

i,
O

=
89 %

R1
O2Et

F.. R=RI=H 1 R=Me, R =2-methylpropenyl intrarnolecular EtO2C, H ene reaction , eo . ~ S 62 % M retro A Diels-Alder =

M~.~y..SH EtO2C" L ~ CH2

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Baldwin - New thermal method for generating thioaldehydes from alkyl thiosu/finates [82CC 1029]

S.

'40

(1.1)

34

Application of Diels-Alder Cycloaddition Chemistry

New tactics for effecting Diels-Alder reactions Dauben- Cycloadditions at high pressure [80JACS7126, 85JOC2567] ~CO2Me S~ ~ _j,,~O 1)liq HCN 2) H3PO4 3) HCI, AcOH-H20 = ~ s~.~o O + ~ 7 kbar, i1, 24 h (10 g scale) "

~0

4) SOCI2, A 50 %

O O~o

Ra-Ni, EtOAc ,%3 h _.~ 51% overall (+8 % epimer)

O ~ ~ O

Canthat~din

Knight - Vinyl furan Diels-Alder reactions [88TL2107]

MeO2C'~"~
290 ~ 100 %
v

MeO2C'~~'~ 290 ~ 97 %

MeOjC/~/,~

Keay - High pressure intramolecular Diels-Alder reaction of furan as a diene [89TL1045] O 12 kbar R R2 25 ~ R, R1, R2 = H, Me 43-65 % McCulloch - Diels-Alder reactions of pyrroles [70CJC1472] CO2Me C AlCla III = C CH2CI2 i COiMe 75 % N,CO2Me R~~ COiMe R2 \ CO2Me R1 AICI3 ~ CO2Me

R2

R1 + i CO2Me

85 % R2f..,,,~n,~CO2 Me

R 1 = H; R2 = Me

H"N'cojMe

Application of Diels-Alder Cycloaddition Chemistry

Kozikowski - Diels-Alder reaction of pyrrole with allene [78JOC2083]
o

35

,r.CO,Et
+ ~ "COjEt 70 %"

/i~N
CO2Et 75 ~ CO2Et CO2Et

/~=N
O2Et J~"\CO2Et CO2Et

N"~

CO2Et

Murase - Vinyl pyrroles as dienes for Die/s-Aider reactions [91CPB489] SCH2Ph S /JL'Me i Me BnCI
THF I Me

.SCH2Ph = ~ /~"CH2 1) 0 2) DDQ

21% overall

Wuonola - Intramolecular [4+2]-cycloaddition of imidazoles [92TL5697] Me"N~N

i~ )

Me

A 220 ~

0 Me Me"N~" N"
N - HCN 7O%

Me ,~

Liotta - Tandem Diels-Alderlretro Die/s-Aider reaction of oxazoles [83TL2473]

N~

O + ---

\ OAc 90 %

= PhC=N + O ~

OAc

Ph

Oxazole cycloadditions - Synthetic equivalent of 2-aza-1,3-dienes

Firestone [67TET943] Me~'~ O + MeSO2~o N~/ ~ ~ 130 75 % MSO2Me . U ~ O - MeSOiH -

OH MeN ~ ~ O

36

Application of Diels-Alder Cycloaddition Chemistry

Jacobi- Intramolecular cycloadditions with oxazoles [84TL4859,92MI001, 81JOC2065, 78JACS7748,90JOC202]

C: Me 0 60 Me Me

%~

H* ==~ 98% = 0
Gnididione

94

~ ' ~ 0/'~0
Paniculide-A

OMe

OMe

S I Retro Oiels-Alder of Oxazoles I

(-) Norsecurinine

Jacobi -Synthesis of furans or functionality derived from a s u ~ u r a n [87TET5475] ~ O~o ~ ,,,,~~N)J~OMe PhEt _ refluxMe

1) NaBH4 ,.

- MeCN
94 %

2) pH5 H

OH..~ O H O
PaniculideA

Application of Diels-Alder Cycloaddition Chemistry

37

Diels-Alder of Thiazole Derivatives Jacobi - Formation of fused ring thiophenes [84HET281, 88TET3327, 87TL2937] Me~OEt N~ ,S OEt

~
I O

-MeCN 57 %

"

R = CH2OMe

H i ~ Me~~O ~ Me 74% Me Ra-Ni_

85 % -

H Me Me

~en~U~ 1'1

Intramolecular Kondrat'eva Pyridine Synthesis [57MI666, 59MI484] Weinreb - Addition of DBN is helpful to intramolecular cycloadditions [89JO05580]

~~1'~ N,,Ac

A o-DCB DBN

.,Ac

[
A -H20 ~NAc

OTBS

OTBS

OTBS

NOTE: oxazolesbearingan EWG at C4are unreactivein cycloadditions.

I Heter~

cti~ I

Cycloadditions involving heteroaromatic azadienes. Review: Boger [86CR781] Sauer [69TL5171]

49--*7./o CO2Me

'pyrrolidine CO2Me

38

Application of Diels-Alder Cycloaddition Chemistry

Boger - Die/s-Aider reactions of heterocyclic azadienes for the total synthesis of complex molecules [87JACS2717] NH CO2Me dioxane 1) H2S,Et2NH ~~~'SMe 80 ~ 22 h NO2 dioxane _- NO2 N + || | 2) Mel, MeCN 82 % MeO" ~'~ 42 % MeO" ~ MeO2C

N)~-N N.,~N

R2N",~M e 4 eq

~OBn
" ~ "OMe
OMe

CH2CI 2, 6.2 Kbar rt, 120 h

, ID,

(2.8" 1)

65 %

M e O ~ IN.< CO2Me [~OBn

~r~ "OMe
OMe

10 steps
I=

NH2~Me

Streptonigrin OMe

Indole as a dienophile in inverse electron demand Die/s-Aider reaction

Snyder [90JOC3257] CO2Me CO2Me

R R=Bz

COtMe

CO2Me

Inverse electron demand 4+2 reactions of pyridazines

Neunhoeffer [73LAC1955] R1 R2"~ R21 R i ~ / N I~1 + Me2N~ CH2 1110Me X = NMe2,OMe 57-93 %
91

NOTE: Dimethylanilinederivative formedpredominantly.

Application of Diels-Alder Cycloaddition Chemistry

Neunhoeffer - Reaction of dimethyl pyridazine 4,5-dicarboxylic acid dimethyl ester with an ynamine [72TL1517, 73LAC437]

39

.C02Me
N~"~CO2 Me MeC_=CNEt2 MeO2CN.~ NEt2 N~,,,,'~CO2Me
Me

-N2

MeO2C,,~~ NEt2 MeO2C" ~ "Me

78MI1095] Sauer [66TL4979] R N"~N N~"N

Inverse electron demand 4+2 reactions of 1,2,4,5-tetrazines [84MI550,

R1CH=CHR 1 =

,,sN R N . I ~ ..R1 1~"TL'..~ H

N

"N2

~RR 1
N .
.,

R
Die/s-Aider reactions of electron deficient heteroaromatic dienes

Roffey [69JHC497], Seitz [79AP452], Sauer [84TL2541, 83TL1481, 75TL2897]

EtO,,,ll/Ph r
NH CO2Me /

,N I~1/CO2Me

"N2 27 %

CO2Me N~I',,N CO2Me

LMeO2C Ph

N-J~N N~IN
I II

CO2Me

"'y"
R = alkyl, Ph

=- "

N.=-~N..NMe2 /

~,bCO~M,, " 1

"N2 = 56-81%

N~,,N.NMe2
CO2Me

CO2Me

Taylor - Route to condensed pyrazines via internal cycloadditions using nitriles as dienophiles [89JOC1245, 86JOC1967] CN Ph,,,,,~N,,N L x

225.235oc

Ph,. N,. ~ X

X = O, NCOCF 3

40

Application of Diels-Alder Cycloaddition Chemistry

2.3 References
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