3-(tributylstannyl)allyl alcohols: Useful building blocks for solid-phase synthesis of skipped dienes and trienes

Article abstract of DOI:10.1135/cccc20000434

Repeated Stille coupling of 3-substituted 3-(tributylstannyl)allyl alcohols 2 on a solid support was used to synthesize a 21 × 21 library of skipped dienes and a 21 × 21 × 21 library of skipped trienes. Starting 3-(tributylstannyl)allyl alcohols were prep

Full text of DOI:10.1135/cccc20000434

434
Havránek, Dvořák:
3-(TRIBUTYLSTANNYL)ALLYL ALCOHOLS: USEFUL BUILDING
BLOCKS FOR SOLID-PHASE SYNTHESIS OF SKIPPED DIENES
AND TRIENES
1
2,
Miroslav HAVRÁNEK and Dalimil DVOŘÁK *
Department of Organic Chemistry, Prague Institute of Chemical Technology, Technická 5,
1
2
166 28 Prague 6, Czech Republic; e-mail: miroslav.havranek@usa.net, dvorakd@vscht.cz
Received Decem ber 21, 1999
Accepted February 25, 2000
Repeated Stille couplin g of 3-substituted 3-(tributylstan n yl)allyl alcoh ols 2 on a solid sup-
port was used to syn th esize a 21 × 21 library of skipped dien es an d a 21 × 21 × 21 library of
skipped trien es. Startin g 3-(tributylstan n yl)allyl alcoh ols were prepared by Pd-catalyzed
h ydrostan n ation of substituted prop-2-yn -1-ols, by h ydroalum in ation by LiAlH4 followed
with tran sm etallation to tin usin g tributyltin m eth oxide, or by substitution of ch lorin e in
(Z)-6-ch loro-3-(tributylstan n yl)h ex-2-en -1-ol with appropriate n ucleoph ile. Syn th esized li-
braries were tested for th e activity to en dorph in receptors, but with n egative results.
Key w ord s: Com bin atorial ch em istry; Libraries of structures; Stille couplin g; Stan n an es;
Cross-couplin g reaction s; Solid-ph ase syn th esis; Hydroalum in ation .
Oligom ers with –C(R)=CH–CH2– repeatin g un its can , to som e exten t, re-
sem ble th e peptide ch ain con tain in g –CO–CH(R)–NH– fragm en ts (Fig. 1).
Such oligom ers m ay therefore interact with endorphin receptors (µ, K, σ or ρ).
Com bin atorial syn th esis on solid support would be probably th e best
m eth od to fin d poten tially active com poun d of th is type.
Th e Heck, Suzuki an d Stille reaction s are particularly useful for th e con -
struction of libraries1–3 based on th e C–C bon d form ation , as discussed in
R1
O
R3
H
H
N
N
N
N
H
H
O
R2
O
R1
R3
R2
FIG. 1
Com parison of structures of th e peptide ch ain an d th at of a skipped polyen e
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

3-(Tributylstannyl)allyl Alcohols
435
recen t reviews4. Th is m eth odology was also used for solid-ph ase syn th esis
of dien es5.
A possible route to skipped polyen es outlin ed in Fig. 1 is based on th e re-
peated Stille couplin g of 3-(tributylstan n yl)allyl alcoh ols 2 wh ich serve as
buildin g blocks. Th e polym er-attach ed 4-iodoben zoic acid (1) is first cou-
pled with 3-substituted 3-(tributylstan n yl)allyl alcoh ol 2. Th e product 3 is
th en con verted to th e correspon din g ch loride 4 an d coupled with an oth er
stan n an e 2 givin g dien e 5. Repetition of th e last two steps would th en give
h igh er oligom ers like 6 (Sch em e 1).
RESULTS AND DISCUSSION
Th e idea of repeated couplin g was first tested by syn th esis of dien es in solu-
tion . Th us couplin g of m eth yl 4-iodoben zoate (24) with (Z)-3-(tributyl-
stan n yl)but-2-en -1-ol (2b) in th e presen ce of PdCl2(PPh 3)2, gave cin n am yl
alcoh ol 25b in 53% yield. Tran sform ation of th e alcoh ol to th e correspon d-
in g ch loride with PPh 3 an d CCl4 proceeded in 80% yield. Th e resultin g allyl
ch loride reacted with an oth er (Z)-3-(tributylstan n yl)but-2-en -1-ol (2b) in
th e presen ce of Pd2(dba)3·CHCl3/AsPh 3, affordin g dien e 26b in 70% yield.
Th e (Z)-con figuration of th e double bon d of 2b rem ain s un ch an ged durin g
th e couplin g reaction . Th e sam e reaction sequen ces were repeated with
(Z)-3-ph en yl-3-(tributylstan n yl)prop-2-en -1-ol (2c). In th is case th e first
couplin g proceeds with on ly 35% yield usin g PdCl2(PPh 3)2 as a catalyst.
However, wh en Herrm an n m etallacyclic catalyst6 7 was used, th e couplin g
product 25c was obtain ed in 65% yield (Sch em e 2). Con version of 25c to
ch loride an d couplin g with an oth er 2c furn ish ed dien e 26c in 47% overall
yield, in th is case as a m ixture of E an d Z isom ers.
Synthesis of Building Blocks
For assem blin g th e desired library, syn th esis of diverse selection of
stan n an es 2 was crucial. Th erefore stan n an es 2a–2v with various side-ch ain
substituen ts were prepared (Sch em e 1).
Stan n an es 2a–2j were prepared from correspon din g prop-2-yn -1-ols by
h ydroalum in ation with LiAlH4, followed by tran sm etalation to tin 7. Due to
th e in com patibility of m an y fun ction al groups with LiAlH4, th e stan n an es
bearin g fun ction al groups h ad to be prepared by differen t m eth ods. Th e key
in term ediate for preparation of th e stan n an es 2l–2p was stan n an e 9 wh ich
was prepared from eth yl 6-ch loroh ex-2-yn oate (8) by reaction with
Bu3Sn (Bu)Cu(CN)Li2 an alogous to th at described for th e trim eth ylstan n yl
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

436
Havránek, Dvořák:
O
O
O
Bu3Sn
OH
P
O
P
O
CH3O
R1
Pd cat.
2
(i)
OH
OH
3
1
25
I
R1
R1
O
P
O
2, 3, 4, 25 config. R1, R2, R3
config.
Z
Z
Z
Z
Z
E
Eb
Eb
Eb
Eb
R1, R2, R3
C6H5O(CH2)3
NC(CH2)3
O(CH2CH2)2N(CH2)3
(EtO2C)2CH(CH2)3
TsNH(CH2)3
2, 3, 4, 25
a
b
c
d
e
f
Z
Z
Z
Za
Z
Z
Za
Z
H
CH3
Ph
l
m
n
o
p
r
s
t
u
v
X
4
(CH3)3Si
n-C5H11
(CH3)2CH
2-thienyl
4-CH3OC6H4
CH3OCH2CH2
C6H5CH2OCH2
THPOCH2
R1
H
X = OTf, OTs, Cl,
OAc, OCOCF3
g
h
i
j
k
C6H5CONHCH2
BocNHCH2
3-FC6H4CONHCH2
CH3CONHCH2
Z
Za
Za
Bu3Sn
R2
OH
a Configuration of corresponding compounds 3, 4 and 25 is E,
b Configuration of corresponding compounds 3, 4 and 25 is Z
(ii)
2
O
O
O
P
O
P
OH
OH
R1
R1
R2
R3
R2
5
6
O
O
(i)
(i)
CH3O
CH3O
OH
OH
R1
R1
R2
R3
R2
27
27a, R1= R2= R3= CH3
26
26b, R1= R2= CH3
26c, R1= R2= Ph
.
(i) CH3ONa, CH3OH; (ii) Pd2(dba)3 CHCl3, P(2-tolyl)3, NMP
Compounds 25a-25d and 26b, 26c were fully characterized; compound 27a was characterized by
1H NMR and MS; compounds 25e-25v cleaved from the polymer were of more than 78% purity
(HPLC) and were not further characterized; using stannanes 2a-2v 21 x 21 library of dienes 5 and
26 and 21 x 21 x 21 library of trienes 6 and 27 were synthetized.
SCHEME 1
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3-(Tributylstannyl)allyl Alcohols
437
O
O
O
Bu3Sn
R
OH
H3CO
H3CO
H3CO
several
steps
2b, 2c
OH
OH
Pd cat.
I
24
R
R1
R2
26b, R1 = R2 = CH3, 70%
26c, R1 = R2 = Ph, 47%
Ar2
P
25b, R = CH3, PdCl2(PPh3)2 (3 mol%),
O
O
O
yield = 53%
Pd
Pd
25c, R = Ph, PdCl2(PPh3)2 (3 mol%),
P
O
yield = 35%
Ar2
25c, R = Ph, cat. 7 (0.2 mol%),
yield = 65%
7, Ar = 2-tolyl
SCHEME 2
derivative8 an d subsequen t reduction 9 with DIBAL-H. Nucleoph ilic dis-
placem en t of th e ch lorin e atom by appropriate n ucleoph ile th en furn ish ed
th e desired substituted stan n an es 2l–2p (Sch em e 3).
(i)
(ii)
Cl
Cl
CO2Et
Cl
CH2OH
CO2Et
Bu3Sn
Bu3Sn
Nu
8
9
2l, Nu = PhO (63%)
2m, Nu = CN (75%)
2o, Nu = (EtO2C)2CH
2p, Nu = TsNH
2n, Nu = morpholine (70%)
(i) 1. Bu3Sn(Bu)Cu(CN)Li2, 2. H2O, NH3, NH4Cl; (ii) DIBAL-H
SCHEME 3
Nu
CH2OH
Bu3Sn
2l - 2p
Stan n an es 2k an d 2t were prepared by reaction of correspon din g
alkyn oates with tributylstan n ylcuprate10 followed by reduction of th e ester
group with DIBAL-H (Sch em e 4). Th e startin g ester 11 was prepared by
dilith iation of 3-(N-tert-butoxycarbon ylam in o)prop-1-yn e11 followed by re-
action with carbon dioxide an d esterification with diazom eth an e.
BocHN
Bu3Sn
OH
Bu3Sn
THPO
OH
Y
(i)
(ii)
CO2R
2k
2t
10, R = C2H5, Y = THPO
11, R = CH3, Y = BocNH
.
(i) 1. Bu3Sn(Bu)Cu(CN)Li2, BF3 Et2O; 2. H2O, NH3, NH4Cl; 3. DIBAL-H
(ii) 1. Bu3Sn(Bu)Cu(CN)Li2, MeOH; 2. H2O, NH3, NH4Cl; 3. DIBAL-H
SCHEME 4
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438
Havránek, Dvořák:
Preparation of stan n an es bearin g th e am ide group started from
4-am in obut-2-yn -1-ol with th e am in o group protected as 2,5-dim eth yl-
pyrrole derivative12 12. Hydroalum in ation followed by reaction with
tributyltin m eth oxide afforded th e desired pyrrolylstan n an e 13 in 42%
yield7. However, all attem pts to rem ove th e 2,5-dim eth ylpyrrolo group
with out splittin g th e tributylstan n yl group failed. Th erefore, th e
pyrrolylalkyn ol 12 was con verted to iodo derivatives 16 an d 17 with th e
aim to replace th e h alogen by tributylstan n yl group by Pd-catalyzed reac-
tion with h exabutyldistan n an e13. To our disappoin tm en t, th is approach
also failed givin g on ly products of dim erization (Sch em e 5).
H2N
(iii)
N
(i)
(ii)
H2N
N
OH
(iv)
OH
Bu3Sn
OH
OH
(vii)
Bu3Sn
12
13
PhCONH
(vi)
H2N
PhCONH
Bu3Sn
N
(iii)
OH
(v)
OH
I
OR
I
OH
I
14
15
16, R = PhCO
17, R = H
(i) (CH3COCH2)2, 96%; (ii) 1. LiAlH4, 2. EtOAc, 3. Bu3SnOCH3, 4. H2O; (iii) NH2OH;
(iv) 1. LiAlH4, 2. EtOAc, 3. I2; (v) PhCOCl; (vi) CH3ONa, CH3OH; (vii) (Bu3Sn)2, Pd cat.
SCHEME 5
Th e am idostan n an es 2s, 2u , 2v an d 21–23 were fin ally prepared by
Pd-catalyzed h ydrostan n ation 14 of th e correspon din g am idopropyn ols
18–20. Th is m eth od gives a m ixture of 2- an d 3-(tributylstan n yl)-
propen -1-ols in rough ly 1 : 1 ratio (Sch em e 6). Th e regioisom ers were sepa-
rated by ch rom atograph y an d th eir structures were determ in ed usin g selec-
1
tively decoupled H NMR.
RCONH
Bu3Sn
2s, R = Ph
OH
RCONH
OH
Bu3SnH
RCONH
OH
+
Pd(PPh3)4
SnBu3
18, R = Ph
21, R = Ph
19, R = 3-FC6H4
20, R = CH3
2u, R = 3-FC6H4
2v, R = CH3
22, R = 3-FC6H4
23, R = CH3
SCHEME 6
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

3-(Tributylstannyl)allyl Alcohols
439
Solid-Phase Synthesis
4-Iodoben zoic acid attach ed to th e h ydroxy-fun ction alized Ten ta Gel resin
(1) (diisopropylcarbodiim ide, 1-h ydroxyben zotriazole, 4-(dim eth ylam in o)-
pyridin e, dich lorom eth an e) was subjected to couplin g reaction s with an ex-
cess of 3-(tributylstan n yl)allyl alcoh ols 2a–2d un der th e con dition s de-
scribed earlier for th e reaction of vin yl- an d aryltin reagen ts (NMP,
Pd2(dba)3·CHCl3, AsPh 3, 45 °C)3a (Sch em e 1). Th e cross-coupled products
were th en cleaved from th e polym er by treatm en t with MeONa in
MeOH–THF an d th e yields of 25a–25d were determ in ed by HPLC (Table I).
Stan dards of th e products for th e HPLC determ in ation were prepared by
couplin g reaction in solution (see Experim en tal).
As can be seen from Table I, con version of 1 was n ot com plete un der
th ese con dition s. Th ere is a sign ifican t differen ce between th e reaction in
solution an d on a solid support. Th us th e couplin g of 2d with m eth yl
4-iodoben zoate in solution (Pd2(dba)3/AsPh 3) gave 90% yield of th e cou-
plin g product 25d , wh ile on a solid support th e yield was on ly 31% un der
oth erwise iden tical con dition s. In crease in tem perature did n ot im prove
yields an d th erefore th e in fluen ce of various ligan ds was exam in ed n ext us-
in g 2b as a m odel com poun d. Th e best results were fin ally ach ieved usin g
Herrm an n catalyst 7 in con cen tration of 0.3 m ol% at 100 °C. Un der th ese
con dition s, n ot on ly h igh yield of th e couplin g product was obtain ed, but
also th e con version of startin g iodoben zoate was quan titative (Table I).
TABLE I
Couplin g of 4-iodoben zoic acid attach ed to polym eric support 1 with stan n an esa 2a–2d
(Sch em e 1) catalyzed with Pd2(dba)3·CHCl3/AsPh 3 an d Herrm an n catalyst 7
a
Pd2(dba)3/AsPh 3
Yieldc,
Catalyst 7b
R
Stan n an e
Product
Un reacted 1,
Yieldc,
Un reacted 1,
%
%
%
%
H
2a
2b
2c
2d
25a
25b
25c
25d
90
80
71
50
0
5
89
78
91
74
0
0
0
0
Me
Ph
20
Me3Si
trace
a
Reaction con dition s: Pd2(dba)3·CHCl3 (12 m ol%) : AsPh 3 (48 m ol%), NMP, 45 °C, 20 h .
Reaction con dition s: 7 (0.3 m ol%), NMP, 100 °C, 14 h . HPLC yield.
b
c
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440
Havránek, Dvořák:
For couplin g with an oth er stan n an e, activation of th e polym er-attach ed
allyl alcoh ol obtain ed in th e previous step was n ecessary. Con version to th e
correspon din g ch loride, acetate, tosylate, trifluoroacetate an d triflate was
exam in ed. Due to h igh reactivity of th ese derivatives, it was n ot possible to
obtain th e yields of th e polym er-attach ed activated products directly. Th e
yields were th erefore determ in ed after th e secon d couplin g step in wh ich
th e polym er-boun d alcoh ol 3b, stan n an e 2b an d catalyst 7 were used.
Ch lorides, prepared from th e alcoh ols by th e reaction with PPh 3 an d CCl4,
were foun d to give gen erally th e best results.
Th e couplin g of such prepared polym er-boun d allyl ch loride with th e
n ext stan n an e was optim ized in th e preparation of th e dien es 26b an d 26c.
In th is case Pd2(dba)3·CHCl3/tris(2-tolyl)ph osph in e (PdL2) in NMP at 80 °C
gave th e best results affordin g dien es 26b an d 26c in 55 an d 50% overall
yields, respectively, based on th e startin g iodoben zoate 1 (Sch em e 1). Syn -
th esis of trien e 27 by exten sion of th is m eth od was also successful. Trien e
27 was obtain ed as a m ixture of in separable isom ers in 95% purity (HPLC).
Th e above described optim ized m eth od was used for th e com bin atorial
syn th esis usin g twen ty-on e stan n an es 2a–2v an d th e resin -boun d
4-iodoben zoate (1). To en sure quan titative con sum ption of 1 in th e reac-
tion with all stan n an es 2a–2v, th e 1 m ol% of th e catalyst 7 was used an d
th e reaction tem perature was in creased to 110 °C. After th e first couplin g
step, th e product was cleaved from a sm all part of each sam ple an d an a-
lyzed by HPLC. As eviden t from th e HPLC data (Table II), th e couplin g pro-
TABLE II
HPLC reten tion tim ea (t) an d purity of products obtain ed by couplin g of stan n an es 2a–2v
with polym er-supported 4-iodoben zoate (1)
Stan n an e t, m in Purity, % Stan n an e t, m in Purity, % Stan n an e t, m in Purity, %
2a
2b
2c
2d
2e
2f
4.24
4.67
93
93
92
92
97
83
95
2h
2i
9.10
4.19
7.16
5.58
16.80
3.48
–
94
91
91
96
95
93
–
2o
2p
2r
4.93
5.54
4.63
3.93
5.37
4.36
2.96
79
78
85
95
90
95
93
8.33
2j
11.71
20.83
9.42
2k
2l
2s
2t
2m
2n b
2u
2v
2g
7.13
a
b
Reverse-ph ase C-18, m eth an ol–water 76 : 24. Th e product did n ot pass th rough th e colum n ,
TLC (silica gel, CHCl3–EtOH–aqueous NH3 85 : 14 : 1) sh owed on ly on e spot.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

3-(Tributylstannyl)allyl Alcohols
441
ceeds very clean ly, givin g virtually sin gle product in all cases. Th e sam ples
were th en m ixed togeth er, treated with PPh 3/CCl4, divided in to 21 vials,
an d again treated with th e sam e set of twen ty-on e stan n an es. Each sam ple
was again divided in to two parts an d a cleavage of th e products from on e
part afforded 21 × 21 library of dien es. With th e rest, th e wh ole process was
repeated givin g 21 × 21 × 21 library of trien es.
Th e easiest way to furth er in crease diversity of th e above libraries of
dien es an d trien es is to use differen tly substituted iodoben zoic acids. Th ere-
fore polym er-attach ed 3-iodoben zoic (28b), 3-iodo-4-m eth ylben zoic (28c)
an d 2-[N-(tert-butyloxycarbon yl)am in o]-5-iodoben zoic (28d ) acids were
subjected to th e reaction with stan n an es 2b, 2c an d 23 un der th e above
con dition s used for couplin g of th e polym er attach ed 1 (Sch em e 7). As evi-
Ar2
OH
O
H3CCONH
OH
23
2b
O
P
(i)
Ar1
Ar2
(i)
H3C
31a-31d
1, 28b-28d
25b, 29b-29d
2c
(i)
28
b
Ar1
29, 30, 31
Ar2
a
b
H3CO2C
H3CO2C
Ar2
OH
I
Ph
c
d
CH3
25c, 30b-30d
I
BocHN
c
d
H3CO2C
CH3
BocHN
H3CO2C
I
(i) 1. cat. 7, NMP, 100 oC; 2. CH3ONa, CH3OH
SCHEME 7
den t from HPLC an alysis of th e products freed from th e polym er, all cou-
plin gs proceeded with 100% con version (n o m eth yl ester of th e startin g
substituted iodoben zoic acid was observed after m eth an olysis) an d th e
products were very pure (Table III). Structure of com poun ds 31a–31d was
1
con firm ed by H NMR an d MS.
In con clusion , th e m eth odology suitable for th e repeated Pd-catalyzed
couplin g of 3-(tributylstan n yl)allyl alcoh ols on solid support was developed.
Th is m eth odology was used for th e com bin atorial syn th esis of a 21 × 21 li-
brary of skipped dien es an d 21 × 21 × 21 library of skipped trien es. Both th e
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

442
Havránek, Dvořák:
obtain ed libraries were tested for th eir activity to th e en dorph in receptors,
but with n egative results.
EXPERIMENTAL
All reaction s were perform ed un der dry argon atm osph ere. THF was distilled from ben zoph e-
n on e ketyl un der N2 atm osph ere just prior to use. 1H NMR spectral data were recorded on a
Varian Gem in i spectrom eter at 300 MHz, 13C NMR at 100.6 MHz, ch em ical sh ifts (δ-scale)
are reported in ppm an d couplin g con stan ts (J) in Hz. IR spectra (waven um bers in cm –1
)
were recorded on a Nicolet 750FT-IR spectrom eter. Mass spectra were recorded on a ZAB-SEQ
(VG An alytical) spectrom eter. HPLC an alyses were run on reverse ph ase LiCh rosph er 100
RP-18, 120 m m with m eth an ol–water 76 : 24–85 : 15 as a m obile ph ase. HPLC yields were
TABLE III
Couplin g of polym er-supported iodoben zoic acids 1 an d 28b–28d with stan n an es 2b, 2c
an d 23
Polym er
supported
iodoben zoic acid
HPLC yield/HPLC purity
%
Reten tion tim e
m in
Stan n an e
Product
1
2b
2c
23
25b
25c
31a
78/93a
91/93c
–/93d
4.67b
4.24b
3.85b
28b
28c
28d
2b
2c
23
29b
30b
31b
88/94e
–/94
4.82b
5.97e
3.26
–/87d
2b
2c
23
29c
30c
31c
>95/94c
–/83
5.95b
7.15e
3.67b
–/88
2b
2c
23
29d
30d
31d
62/91a
–/85
7.50f
12.42f
9.56b
–/65d
a
Product ch aracterized by com parison with auth en tic com poun d prepared by th e sam e reac-
b
c
tion in solution . Meth an ol–water 76 : 24. Product ch aracterized by com parison with au-
th en tic com poun d prepared by direct Pd-catalyzed couplin g of h ydroalum in ated
d
alk-2-yn -1-ol with appropriate iodoben zoate in THF solution 15
.
Product ch aracterized by
MS an d 1H NMR. Meth an ol–water 80 : 20. Meth an ol–water 85 : 15.
e
f
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

3-(Tributylstannyl)allyl Alcohols
443
obtain ed usin g auth en tic sam ples prepared by th e reaction s in solution with ben zoph en on e
or 2-m eth yln aph th alen e as an in tern al stan dard. HPLC purity refers to th at obtain ed from
th e peak in tegrals of th e peaks at 254 n m . Stan n an es 2a –2j, 13 (ref.7), 2r (ref.14d ),
eth yl-6-ch loroh ex-2-yn oate9 (8), eth yl [(4-tetrah ydropyran -2-yl)oxy]but-2-yn oate16 (10),
N-(tert-butyloxycarbon yl)prop-2-yn -1-ylam in e11, 4-(2,3-dim eth ylpyrrol-1-yl)but-2-yn -1-ol7 (12),
4-ben zam idobut-2-yn -1-ol17, 4-acetam idobut-2-yn -1-ol17 were prepared accordin g to th e re-
ported procedures. Ten ta Gel S OH (capacity 0.030 m m ol/g) was purch ased from RAPP
Polym ere Gm bH. Activities of th e obtain ed libraries were tested in th e Torrey Pin es In stitute
for Molecular Studies.
Synthesis of Cinnamyl Alcohols and Dienes in Solution
(Z)-3-[4-(Meth oxycarbon yl)ph en yl]but-2-en -1-ol (25b)
Meth yl 4-iodoben zoate (24; 0.524 g, 2 m m ol), (Z)-3-(tributylstan n yl)but-2-en -1-ol (2b ;
0.765 g, 2.1 m m ol) an d PdCl2(PPh 3)2 (0.042 g, 0.06 m m ol) were dissolved in 3 m l of DMF
an d h eated un der argon at 100 °C for 3 h . Th e m ixture was th en poured in to an aqueous so-
lution of potassium fluoride, eth er was added an d th e m ixture was vigorously sh aken to re-
m ove tributyltin iodide. Th e organ ic layer was separated an d th e aqueous ph ase was
extracted with eth er. Th e com bin ed organ ic layers were dried over m agn esium sulfate, eth er
was evaporated an d th e residue was ch rom atograph ed on silica (radial ch rom atograph y).
Elution with petroleum eth er–eth er–aceton e 5 : 3 : 2 afforded 0.219 g (53%) of th e product
as an oil. 1H NMR (CDCl3): 8.00 d, 2 H, J = 8.2 (Ar); 5.76 dt, 1 H, Jt = 7.0, Jd = 1.5
(=CH-CH2OH); 4.05 d, 2 H, J = 7.1 (-CH2OH); 3.91 s, 3 H (COOCH3); 2.09 s, 3 H (CH3).
IR (CHCl3): 3 620, 3 467, 3 018, 2 976, 2 927, 2 895, 1 713, 1 608, 1 437, 1 391, 1 284, 1 047,
877. For C12H14O3 (206.2) calculated: 69.89% C, 6.84% H; found: 69.53% C, 6.94% H. 13C NMR
(CDCl3): 167.6 s; 146.3 s; 139.9 s; 127.2–131.1 m ; 60.8 t, J = 142; 52.8 q, J = 146; 25.7 dq, Jq
127, Jd = 6.9 – th is in teraction correspon ds with cis relation of CH3 an d =C-H.
=
(Z)-1-Ch loro-3-[4-(m eth oxycarbon yl)ph en yl]but-2-en e
A m ixture of (Z)-3-[4-(m eth oxycarbon yl)ph en yl]but-2-en -1-ol (25b ; 0.453 g, 2.2 m m ol),
triph en ylph osph in e (0.603 g, 2.3 m m ol), dich lorom eth an e (5 m l) an d tetrach lorom eth an e
(3 m l) was stirred at room tem perature overn igh t. Th e solven ts were th en evaporated an d
th e residue was ch rom atograph ed on silica (radial ch rom atograph y). Elution with petroleum
eth er–eth er–aceton e 8 : 1 : 1 gave 0.394 g (80%) of th e desired ch loride as an oil. 1H NMR
(CDCl3): 8.03 d, 2 H, J = 8.8 (Ar); 7.26 d, 2 H, J = 8.3 (Ar); 5.77 qt, 1 H, J1 = 8.2, J2 = 1.7
(=CH); 3.88 d, 2 H, J = 8.8 (-CH2Cl); 3.93 s, 3 H (-COOCH3); 2.10 s, 3 H, (CH3-C=).
IR (CHCl3): 3 027, 2 954, 1 720, 1 610, 1 438, 1 261, 1 117, 1 019, 864. For C12H13ClO2
(224.7) calculated: 64.15% C, 5.83% H, 15.78% Cl; foun d: 63.91% C, 5.99% H, 15.41% Cl.
(Z,Z)-6-[4-(Meth oxycarbon yl)ph en yl]-3-m eth ylh epta-2,5-dien -1-ol (26b)
A solution of (Z)-1-ch loro-3-[4-(m eth oxycarbon yl)ph en yl]but-2-en e (0.113 g, 0.5 m m ol),
stan n an e 2b (0.180 g, 0.5 m m ol), Pd2(dba)3·CHCl3 (0.007 g, 1.5 m ole %) an d triph en yl-
arsin e (0.009 g, 6 m ol%) in 1-m eth ylpyrrolidin -2-on e (2 m l) was h eated un der argon at
40 °C for 24 h an d worked up as described above for th e preparation of 25b. Th e crude
product was purified by preparative HPLC (reverse ph ase C-18). Th e product was obtain ed as
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a colorless oil (0.092 g, 70%). 1H NMR (CDCl3): 7.96 d, 2 H, J = 8.3 (Ar); 7.41 d, 2 H (Ar); 5.77 t,
1 H, J = 7.4 (=CH-); 5.49 t, 1 H, J = 6.9 (=CH-); 4.17–4.23 m , 2 H (-CH2OH); 3.90 s, 3 H
(COOCH3); 2.98 d, 2 H, J = 7.1 (=CH-CH2-C=); 2.09 s, 3 H (CH3); 1.77 s, 3 H (CH3); 1.38–1.45 m ,
1 H (OH). Th e com poun d con tain ed about 5% of isom er, δ: 8.02, 5.36, 2.71, 2.03, 1.66. IR
(CHCl3): 3 611, 3 018, 2 953, 1 716, 1 606, 1 437, 1 282, 1 116, 969. For C12H20O3 (260.3)
calculated: 73.82% C, 7.74% H; foun d: 73.69% C, 7.81% H.
(Z)-3-[4-(Meth oxycarbon yl)ph en yl]-3-ph en ylprop-2-en -1-ol (25c)
Meth yl 4-iodoben zoate (24; 0.131 g, 0.5 m m ol), (Z)-3-ph en yl-3-(tributylstan n yl)prop-
2-en -1-ol (2c; 0.223 g, 0.53 m m ol) an d th e Herrm an n catalyst (7; 1 m g, 0.001 m m ol) were
dissolved in 1-m eth ylpyrrolidin -2-on e (3 m l) an d h eated un der argon at 110 °C for 3 h . Th e
reaction m ixture was worked up as described for th e preparation of 25b. Ch rom atograph y
on silica gel (radial ch rom atograph y, petroleum eth er–aceton e 95 : 5) gave 0.132 g (73%) of
an oily product. 1H NMR (CDCl3): 8.05 d, 2 H, J = 8.2 (Ar); 7.19–7.34 m , 7 H (Ar); 6.30 t,
1 H, J = 6.9 (=CH-CH2OH); 4.21 d, 2 H, J = 6.6 (-CH2OH); 3.94 s, 3 H (-OCH3). IR (CHCl3):
3 022, 2 955, 1 721, 1 664, 1 487, 1 263, 1 116, 1 020. HR MS (EI), for C17H15O2 (M+ – OH)
calculated: 251.1072; foun d: 251.1177.
(Z)-3-Ch loro-1-[4-(m eth oxycarbon yl)ph en yl]-1-ph en ylprop-1-en e
A m ixture of (Z)-3-[4-(m eth oxycarbon yl)ph en yl]-3-ph en ylprop-2-en -1-ol (3c; 0.170 g, 0.63
m m ol), triph en ylph osph in e (0.190 g, 0.72 m m ol), dich lorom eth an e (2 m l) an d tetrach loro-
m eth an e (1.5 m l) was stirred at room tem perature overn igh t an d th en h eated at 35 °C un til
th e con version was com plete. Th e solven ts were th en evaporated an d th e product (0.132 g,
73%) was obtain ed by preparative TLC on silica gel (petroleum eth er–aceton e 95 : 5).
1H NMR (CDCl3): 8.08 d, 2 H, J = 8.2 (Ar); 7.18–6.78 m , 7 H (Ar); 6.29 t, 1 H, J = 8.2 (=CH);
4.09 d, 2 H, J = 8.2 (-CH2Cl); 3.95 s, 3 H (COOCH3). IR (CHCl3): 3 029, 2 954, 1 721, 1 610,
1 437, 1 263, 1 116. For C17H15ClO2 (286.8) calculated: 71.21% C, 5.27% H, 12.36% Cl;
foun d: 70.97% C, 5.49% H, 12.33% Cl.
6-[4-(Meth oxycarbon yl)ph en yl]-3,6-diph en ylh exa-2,5-dien -1-ol (26c)
(Z)-3-Ch loro-1-[4-(m eth oxycarbon yl)ph en yl]-1-ph en ylprop-1-en e (0.100 g, 0.35 m m ol),
stan n an e 2c (0.184 g, 0.4 m m ol), Pd2(dba)3·CHCl3 (0.005 g, 1.5 m ol%) an d tris(2-tolyl)-
ph osph in e (0.006 g, 6 m ole %) were dissolved in 1-m eth ylpyrrolidin -2-on e (2 m l). Th e m ix-
ture was h eated un der argon at 40 °C for 24 h an d th en worked up as described for prepara-
tion of 25b . Ch rom atograph y on silica (radial ch rom atograph y, petroleum eth er–eth er–
aceton e 8 : 1 : 1) afforded 0.063 g (47%) of th e product as a m ixture of E/Z isom ers.
1H NMR (CDCl3): 8.05 d + 7.87 d (9 : 5), 2 H, J = 8.2, 8.8 (Ar); 7.02–7.23 m , 12 H (Ar);
5.87–6.09 m , 2 H (=CH); 4.20 d + 4.18 d, 2 H, J = 6.6, 5.5 (-CH2OH); 3.95 s + 3.88 s, 3 H
(COOCH3); 3.37 d + 3.33 d, 2 H, J = 7.2, 7.2 (=CH-CH2-C=). IR (CHCl3): 3 020, 2 954, 1 721,
1 438, 1 283, 1 116, 1 020. HR MS (EI), for C26H23O2 (M+ – OH) calculated: 367.1698; foun d:
367.1606.
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(Z)-3-[4-(Meth oxycarbon yl)ph en yl]prop-2-en -1-ol (25a)
Meth yl 4-iodoben zoate (24; 0.131 g, 0.5 m m ol), (Z)-3-(tributylstan n yl)allyl alcoh ol (2a) an d
th e Herrm an n palladium catalyst (7; 1 m g, 0.001 m m ol) were dissolved in 1-m eth yl-
pyrrolidin -2-on e (3 m l). Th e m ixture was h eated un der argon at 110 °C for 3 h an d w as
wo rked u p as d escrib ed fo r p rep arat io n o f 2 5 b . Ch ro m at o grap h y o n silica (rad ial
ch ro m atograph y, petroleum eth er–aceton e 7 : 3) afforded 0.061 g (64%) of th e product.
1H NMR (CDCl3): 8.01 d, 2 H, J = 8.4 (Ar); 7.28 d, 2 H, J = 8.3 (Ar); 6.60 d, 1 H, J = 12.0
(Ar-CH=CH-CH2OH); 5.99 td, 1 H, J1 = 11.8, J2 = 6.3 (Ar-CH=CH-CH2OH); 4.44 dd , 2 H, J1
=
6.5, J2 = 1.7 (-CH2OH); 3.93 s, 3 H (OCH3). IR (CHCl3): 3 615, 3 022, 2 954, 1 718, 1 610,
1 437, 1 285, 1 181, 1 111, 1 017, 866. For C11H12O3 (192.2) calculated: 68.74% C, 6.29% H;
foun d: 68.48% C, 6.33% H.
(Z)-3-[3-Meth oxycarbon yl-4-(tert-butyloxycarbon ylam in o)ph en yl]but-2-en -1-ol
Meth yl 2-(tert-butoxycarbon ylam in o)-3-iodoben zoate (0.188 g, 0.5 m m ol), (Z)-3-(tributyl-
stan n yl)but-2-en -1-ol (2b ; 0.161 g, 0.5 m m ol) an d th e Herrm an n palladium catalyst (7;
1 m g, 0.001 m m ol) were dissolved in 1-m eth ylpyrrolidin -2-on e (2 m l). Th e m ixture was
h eated un der argon at 110 °C for 3 h an d th en worked up as described for 25b. Ch rom atog-
raph y on silica (radial ch rom atograph y, petroleum eth er–eth er–aceton e 8 : 1 : 1) afforded
0.114 g (71%) of th e product. 1H NMR (CDCl3): 10.23 s, 1 H (NH); 8.42 d, 1 H, J = 8.8 (Ar);
7.8 d, 1 H, J = 2.2 (Ar); 7.33 dd, 1 H, J1 = 8.8, J2 = 2.2 (Ar); 5.72 t, 1 H, J = 6.9 (=CH-CH2OH);
4.07 t, 2 H, J = 6.0 (-CH2OH); 3.92 s, 3 H (COOCH3); 2.06 s, 3 H (-CH3); 1.53 s, 9 H
(-C(CH3)3). IR (CHCl3): 3 324, 3 017, 2 983, 1 724, 1 694, 1 582, 1 518, 1 369, 1 310, 1 249,
1 157. For C17H23NO5 (321.4) calculated: 64.54% C, 7.21% H, 4.36% N; foun d: 64.82% C,
7.74% H, 4.30% N.
(E)-3-[4-(Meth oxycarbon yl)ph en yl]-3-trim eth ylsilylprop-2-en -1-ol (25d )
Meth yl 4-iodoben zoate (24; 0.131 g, 0.5 m m ol), (Z)-3-(tributylstan n yl)allyl alcoh ol (2d ;
0.5 g, 1.19 m m ol), Pd2(dba)3·CHCl3 (0.012 g, 0.011 m m ol) an d AsPh 3 (0.0153 g, 0.050
m m ol) were dissolved in 1-m eth ylpyrrolidin -2-on e (6 m l). Th e m ixture was h eated un der ar-
gon at 110 °C for 3 h an d worked up as described for preparation of 25b. Ch rom atograph y
on silica (radial ch rom atograph y, petroleum eth er–eth er–aceton e 80 : 10 : 10) afforded
0.109 g (78%) of th e product. 1H NMR (CDCl3): 7.97 d, 2 H, J = 8.2 (Ar); 7.0 d, 2 H, J = 8.2
(Ar); 6.15 t, 1 H, J = 6.0 (=CH-CH2OH); 3.99 d, 2 H, J = 6.0 (-CH2OH); 3.91 s, 3 H (CH3);
0.07 s, 9 H (-Si(CH3)3). IR (CHCl3): 3 615, 3 014, 2 956, 1 718, 1 605, 1 437, 1 287, 1 115,
1 019, 914, 839. For C14H20O3Si (264.4) calculated: 63.60% C, 7.62% H; foun d: 63.19% C,
7.85% H.
Synthesis of Stannanes 2 and Their Precursors
(Z)-6-Ch loro-3-(tributylstan n yl)h ex-2-en -1-ol (9)
A solution of 1.6 M butyllith ium (7.3 m l, 11.6 m m ol) was added to a suspen sion of copper
cyan ide (0.519 g, 5.8 m m ol) in tetrah ydrofuran (20 m l) at –78 °C. Th e flask was rem oved
from th e coolin g bath an d stirred un til all th e copper cyan ide was dissolved, th e m ixture
was th en again cooled to –78 °C an d tributyltin h ydride (3.1 m l, 11.6 m m ol) was added. Th e
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Havránek, Dvořák:
form ed yellow solution was stirred at –78 °C for 10 m in an d boron trifluoride eth erate
(0.74 m l, 5.8 m m ol) was added followed after 5 m in with eth yl 6-ch loroh ex-2-en oate (8;
0.923 g, 5.3 m m ol). Th e resultin g m ixture was stirred at –78 °C for 1 h an d at –40 °C for an -
oth er 1.5 h . Th e resultin g deep red solution was poured to an aqueous am m on ia an d am m o-
n ium ch loride. Eth er was added an d th e m ixture was sh aken un til th e aqueous ph ase was
deep blue. Th e organ ic layer was separated an d th e aqueous ph ase was extracted twice with
eth er. Com bin ed organ ic layers were dried over an h ydrous sodium sulfate, th e solven ts were
rem oved un der reduced pressure an d th e residue was dried in h igh vacuum . Th en it was dis-
solved in an h ydrous eth er (70 m l), cooled to –78 °C an d 1 M diisobutylalum in ium h ydride
(18 m l, 18 m m ol) in h exan e was slowly added. Th e m ixture was stirred at –78 °C for 1 h
an d at –40 °C for an oth er 1.5 h . Meth an ol (5 m l) was added, an d reaction was left to warm
to 0 °C an d saturated solution of am m on ium ch loride (5 m l) was added. After 15 m in th e
m ixture was filtered th rough celite, th e precipitate was wash ed th ree tim es with eth er, th e
solven ts were rem oved un der reduced pressure an d th e residue ch rom atograph ed on silica
(120 g). Elution with petroleum eth er–aceton e 96 : 4 afforded 1.677 g (75%) of th e stan n an e 9
as a colorless oil. 1H NMR (CDCl3): 6.28 t, 1 H, J = 6.6, 3J(Sn -H,trans) = 126 (=CH); 4.06 t, 2 H,
J = 6.6 (CH2OH); 3.51 t, J = 6.6 (CH2Cl); 2.36 t, 2 H, J = 7.4, 3J(Sn-H) = 45 (CH2C=); 1.80 quintet,
2 H, J = 7.4 (CH2CH2CH2); 1.23–1.61 m , 12 H (Sn CH2CH2CH2CH3); 1.16 t, 1 H, J = 5.5 (OH);
0.78–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3): 147.94, 65.59, 44.97,
38.14, 33.50, 29.89, 28.06, 11.29 (CH2, C); 140.38, 12.95 (CH3, CH). IR (CHCl3): 3 612, 3
455, 3 012, 2 958, 2 928, 2 872, 2 854, 1 462, 1 378, 1 072, 990, 864. For C18H37ClOSn
(423.6) calculated: 51.03% C, 8.80% H, 8.73% Cl; foun d: 51.15% C, 8.70% H, 8.31% Cl.
(Z)-6-Ph en oxy-3-(tributylstan n yl)h ex-2-en -1-ol (2l)
Ph en ol (0.168 g, 2 m m ol) an d sodium h ydride (0.060 g, 80%, 2 m m ol) were m ixed in DMF
(3 m l). After all NaH was dissolved, a solution of stan n an e 9 (0.423 g, 1 m m ol) in DMF
(1 m l) was added. Th e reaction m ixture was h eated at 50 °C for 14 h , th en poured in to wa-
ter, extracted with eth er (3 ×) an d com bin ed eth ereal layers were dried over an h ydrous so-
dium sulfate. Ch rom atograph y on 15 g of silica (petroleum eth er–aceton e 96 : 4) afforded
0.303 g (63%) stan n an e 2l as a colorless oil. 1H NMR (CDCl3): 7.24–7.32 m , 2 H (Ar);
6.86–6.97 m , 3 H (Ar); 6.28 t, 1 H, J = 6.6, 3J(Sn -H,trans) = 124 (=CH); 4.05 t, 2 H, J = 5.8
(CH2OH); 3.95 t, 2 H, J = 6.6 (Ph OCH2); 2.40 t, 2 H, J = 7.7 (CH2C=); 1.82 quin tet, 2 H, J =
7.1 (CH2CH2CH2); 1.30–1.60 m , 12 H (Sn CH2CH2CH2CH3); 1.17 t, 1 H, J = 5.5 (OH);
0.75–1.10 m , 15 H (Sn CH2CH2CH2CH3).13C NMR, APT (CDCl3): 159.76, 149.00, 67.78,
65.74, 37.45, 30.45, 29.93, 28.10, 11.28 (CH2, C); 139.80, 13.12, 121.27, 115.24, 14.37 (CH3,
CH). IR (CHCl3): 3 611, 3 013, 2 959, 2 928, 2 873, 2 854, 1 600, 1 586, 1 497, 1 487, 1 377,
1 247, 1 078, 1 041, 994. MS (EI), m/z: 425.1 (M+ – C4H9).
(Z)-6-Cyan o-3-(tributylstan n yl)h ex-2-en -1-ol (2m )
Stan n an e 9 (0.296 g, 0.7 m m ol) an d sodium cyan ide (0.049 g, 1 m m ol) were m ixed in DMF
(4 m l) an d h eated at 60 °C. After 14 h th e reaction m ixture was poured in to water, extracted
with eth er (3 ×) an d com bin ed eth ereal layers were dried over an h ydrous sodium sulfate.
Ch rom atograph y on 10 g of silica (petroleum eth er–aceton e 90 : 10) afforded 0.217 g (75%)
of stan n an e 2m as a colorless oil. 1H NMR (CDCl3): 6.28 t, 1 H, J = 6.3, 3J(Sn -H,trans) = 121
(=CH); 4.07 t, 2 H, J = 5.8 (CH2OH); 2.28–2.40 m , 4 H (CH2CN, =C-CH2CH2); 1.69 quin tet,
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2 H, J = 7.3 (CH2CH2CH2); 1.25–1.53 m , 12 H (Sn CH2CH2CH2CH3); 1.23 t, 1 H, J = 5.5
(OH); 0.82–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3): 147.00, 120.31,
65.44, 39.85, 29.90, 28.08, 26.14, 17.14, 11.30 (CH2, C); 141.16, 14.36 (CH3, CH). IR (CHCl3):
3 611, 3 021, 2 959, 2 928, 2 872, 2 854, 2 250, 1 460, 1 377, 1 074, 996. For C19H37NOSn
(414.2) calculated: 55.10% C, 9.00% H, 3.38% N; foun d: 55.02% C, 8.77% H, 3.56% N.
(Z)-6-Morph olin o-3-(tributylstan n yl)h ex-2-en -1-ol (2n )
Stan n an e 9 (0.296 g, 0.7 m m ol) was dissolved in m orph olin e (3 m l) an d th e solution was
h eated at 60 °C for 24 h . Th e reaction m ixture was poured in to water, extracted with eth er
(3×) an d com bin ed eth ereal layers were dried an h ydrous over sodium sulfate. Ch rom atograph y
on 10 g of silica (petroleum eth er–eth er–trieth ylam in e 50 : 49 : 1) afforded 0.232 g (70%) of
stan n an e 2n as an oil. 1H NMR (CDCl3): 6.25 t, 1 H, J = 6.6, 3J(Sn -H,trans) = 125 (=CH); 4.05 d,
2 H, J = 6.6 (CH2OH); 3.68–3.75 m , 4 H (CH2-O-CH2); 2.42 bs, 4 H (CH2N); 2.31 t, 2 H, J =
7.4 (CH2N); 2.22 t,
2 H, J = 7.4 (CH2-C=); 1.22–1.58 m , 14 H (CH2CH2CH2,
Sn CH2CH2CH2CH3); 0.82–0.98 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3):
149.29, 67.71, 65.71, 59.45, 54.50, 38.99, 29.93, 28.11, 11.27 (CH2, C); 139.42, 14.38 (CH3,
CH). IR (CHCl3): 3 609, 3 014, 2 959, 2 927, 2 872, 2 857, 2 815, 1 461, 1 377, 1 116, 1 071,
1 003, 862. For C22H45NO2Sn (474.3) calculated: 55.71% C, 9.56% H, 2.95% N; foun d:
55.50% C, 9.41% H, 3.05% N.
(Z)-Dieth yl [6-Hydroxy-4-(tributylstan n yl)h ex-4-en -1-yl]m alon ate (2o)
To a solution of sodium (0.12 g, 5 m m ol) in an h ydrous eth an ol (5 m l), dieth yl m alon ate
(0.9 m l, 6 m m ol) followed by stan n an e 9 (0.423 g, 1 m m ol) were added. Th e resultin g m ix-
ture was h eated un der reflux for 24 h , th en poured in to water an d extracted th ree tim es
with eth er. Com bin ed organ ic layers were dried over an h ydrous sodium sulfate, th e solven t
was evaporated an d ch rom atograph y of th e residue on silica (petroleum eth er–eth er–aceton e
90 : 5 : 5) afforded 0.309 g (56%) of desired stan n an e 2o as a colorless oil. 1H NMR (CDCl3):
6.22 t, 1 H, J = 6.6, 3J(Sn -H,trans) = 126 (=CH); 4.19 q, 4 H, J = 7.1 (CH3CH2O); 4.03 t, 2 H, J =
6.1 (CH2OH); 3.30 t, 1 H, J = 7.4 (CH(COOEt)2); 2.23 t, 2 H, J = 7.4 (CH2C=); 1.86 q, 2 H, J =
7.7 (CHCH2CH2CH2); 1.23–1.52 m , 14 H (CH2CH2CH2, Sn CH2CH2CH2CH3); 1.26 t, 6 H, J =
7.1 (CH3CH2O); 1.17 t, 1 H, J = 5.5 (OH); 0.82–0.95 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR,
APT (CDCl3): 170.13, 149.03, 65.73, 62.02, 40.67, 29.90, 29.05, 28.46, 28.08, 11.26 (CH2, C);
139.57, 52.62, 14.80, 14.36 (CH3, CH). IR (CHCl3): 3 609, 3 016, 2 959, 2 928, 2 872, 2 855,
1 727, 1 463, 1 373, 1 294, 1 181, 1 152, 1 024. For C25H48O5Sn (547.3) calculated: 54.86% C,
8.84% H; foun d: 54.58% C, 8.81% H.
(Z)-N-[6-Hydroxy-4-(tributylstan n yl)h ex-4-en -1-yl]-4-m eth ylben zen e-1-sulfon am ide (2p )
4-Meth ylben zen e-1-sulfon am ide (0.171 g, 1 m m ol) was dissolved in 5 m l an h ydrous DMF,
sodium h ydride (0.021 g (80% in oil), 0.7 m m ol) was added an d th e reaction m ixture was
h eated to 60 °C un til all th e sodium h ydride reacted. A solution of stan n an e 9 (0.254 g, 0.58
m m ol) in 1 m l DMF was th en added to th e resultin g wh ite suspen sion an d th e reaction m ix-
ture was h eated to 80 °C for an oth er 16 h . Th e m ixture was poured in to water an d extracted
twice with ch loroform an d twice with eth er. Com bin ed organ ic layers were dried with an h y-
drous sodium sulfate an d th e solven t was evaporated un der reduced pressure. Ch rom atogra-
ph y of th e residue on 10 g of silica (petroleum eth er–eth er–aceton e 80 : 10 : 10) afforded
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

448
Havránek, Dvořák:
0.241 g (60%) of th e product 2p . 1H NMR (CDCl3): 7.74 d, 2 H, J = 8.3 (Ar); 7.31 d, 2 H, J =
8.2 (Ar); 6.16 t, 1 H, J = 6.6, 3J(Sn -H,trans) = 125 (=CH); 4.35 t, 2 H, J = 6.1 (CH2OH); 4.00 t,
1 H, J = 6.3 (NH); 2.92 q, 2 H, J = 6.8 (HN-CH2); 2.43 s, 3 H (CH3); 2.20 t, 2 H, J = 7.4
(CH2C=); 1.22–1.59 m , 14
H (CH2CH2CH2, Sn CH2CH2CH2CH3); 0.77–1.00 m , 15 H
(Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3): 148.09, 144.10, 137.70, 65.55, 43.28, 37.99,
30.37, 29.88, 28.07, 11.25 (CH2, C); 140.31, 130.43, 127.84, 22.25, 14.37 (CH3, CH). IR
(CHCl3): 3 609, 3 027, 3 015, 2 958, 2 927, 2 872, 2 854, 1 599, 1 463, 1 409, 1 377, 1 331,
1 160, 1 094, 1 076, 987, 814. For C25H45NO3SSn (558.4) calculated: 53.78% C, 8.12% H,
2.51% N, 5.74% S; foun d: 53.83% C, 7.96% H, 2.57% N, 6.41% S.
(Z)-4-[(Tetrah ydropyran -2-yl)oxy]-3-(tributylstan n yl)but-2-en -1-ol7 (2k)
A solution of 1.6 M butyllith ium (1.4 m l, 2.2 m m ol) was added to a suspen sion of copper cy-
an ide (0.098 g, 1.1 m m ol) in tetrah ydrofuran (3 m l) at –78 °C. Th e flask was rem oved from
th e coolin g bath an d stirred un til all th e copper cyan ide dissolved. Th e reaction m ixture was
th en cooled again to –78 °C an d tributyltin h ydride (0.58 m l, 2.2 m m ol) was added fol-
lowed, after 10 m in , by boron trifluoride dieth yl eth erate (0.14 m l, 1.1 m m ol) an d a solu-
tion of eth yl 4-[(tetrah ydropyran -2-yl)oxy]but-2-yn oate16 (10; 0.212 g, 1 m m ol) in THF after
an oth er 5 m in . Th e m ixture was stirred at –78 °C for 1 h an d th en at –40 °C for 1.5 h . Th e
resultin g deep red solution was poured to an aqueous am m on ia an d am m on ium ch loride.
Eth er was added an d th e m ixture was sh aken un til th e aqueous ph ase was deep blue. Th e or-
gan ic layer was separated an d th e aqueous ph ase was extracted twice with eth er. Com bin ed
organ ic layers were dried over an h ydrous sodium sulfate, th e solven ts were rem oved un der
reduced pressure an d th e residue was dried in h igh vacuum . Th en it was dissolved in an h y-
drous eth er (70 m l), cooled to –78 °C an d 1
M diisobutylalum in ium h ydride (3.5 m l,
3.5 m m ol) in h exan e was added slowly. Th e m ixture was stirred at 0 °C for 2 h an d th en a
saturated aqueous solution of am m on ium ch loride (1 m l) was added. After 15 m in , th e m ix-
ture was filtered th rough celite an d th e precipitate was wash ed th ree tim es with eth er. Th e
solven t was rem oved u n der redu ced pressu re an d th e cru d e p rodu ct was p u rified by
ch rom atograph y on 30 g of silica (petroleum eth er–aceton e 95 : 5) furn ish in g 0.160 g (35%)
of stan n an e 2k as a colorless oil. Th e 1H NMR was iden tical with th at described in ref.7.
Meth yl 4-(tert-Butoxycarbon ylam in o)but-2-yn oate10 (11)
A solution of 1.6 M butyllith ium (7.5 m l, 12 m m ol) was added to a solution of 3-(tert-butoxy-
carbon ylam in o)prop-1-yn e11 (0.7785 g, 5 m m ol) in THF (10 m l) at –78 °C. Th e m ixture was
allowed to warm to room tem perature, poured in to a dry ice–THF m ixture an d left stan din g
overn igh t. Th e reaction m ixture was th en diluted with water, acidified with dilute h ydro-
ch loric acid an d extracted th ree tim es with eth er. Com bin ed organ ic layers were dried over
anhydrous m agnesium sulfate and the solvents were evaporated in vacuum . Pure acid (0.663 g,
67%) was obtain ed by ch rom atograph y on silica (petroleum eth er–aceton e 80
: 20).
Esterification with diazom eth an e in eth ereal solution furn ish ed alkyn e 11 (0.670 g, 63%).
Th e 1H NMR spectrum of th e obtain ed product was iden tical with th at described in ref.10
.
(E)-4-(tert-Butoxycarbon ylam in o)-3-(tributylstan n yl)but-2-en -1-ol (2t)
Th is com poun d was syn th esized by th e procedure used for syn th esis of 2k except th at boron
trifluoride eth erate was n ot used. A solution of ester 11 (0.213 g, 1 m m ol) an d m eth an ol
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3-(Tributylstannyl)allyl Alcohols
449
(0.2 m l) in THF was added to a solution of stan n ylcuprate prepared from CuCN (0.098 g, 1.1
m m ol), 1.6 M solution of butyllith ium (1.4 m l, 2.2 m m ol) an d tributyltin h ydride (0.58 m l,
2.2 m m ol). After reduction of th e in term ediate with a 1 M solution of diisobutylalum in ium
h ydride in toluen e an d ch rom atograph y of th e crude product on 30 g of silica (petroleum
eth er–trieth ylam in e 92 : 8), 0.106 g (23%) of stan n an e 2t was obtain ed as colorless oil.
1H NMR (CDCl3): 5.95 t, 1 H, J = 6.6, 3J(Sn -H,cis) = 64 (=CH); 4.62 bs, 1 H (NH); 4.22 d, 2 H,
J = 6.6 (CH2OH); 3.93 d, 2 H, J = 6.1, 3J(Sn -H) = 48 (CH2NH); 1.43 s, 9 H ((CH3)3C-);
1.25–1.60 m , 12 H (Sn CH2CH2CH2CH3); 0.82–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR,
APT (CDCl3): 156.79, 145.75, 58.93, 42.97, 29.96, 28.09, 10.20, 9.95 (CH2, C); 141.77, 29.11,
13.38 (CH3, C). IR (CHCl3): 3 614, 3 452, 3 010, 2 959, 2 928, 2 873, 2 855, 1 704, 1 502,
1 458, 1 367, 1 278, 1 185, 1 007. For C21H43NO3Sn (476.3) calculated: 52.96% C, 9.10% H,
2.94% N; foun d: 53.01% C, 8.80% H, 3.06% N.
4-(2,5-Dim eth ylpyrrol-1-yl)-3-iodobut-2-en -1-ol (14)
To a solution of 4-(2,5-dim eth ylpyrrol-1-yl)but-2-yn -1-ol (12; 3.26 g, 20 m m ol) in THF, 0.8
M
THF solution of LiAlH4 (27.5 m l, 22 m m ol) was added dropwise at 0 °C. Th e reaction m ix-
ture was stirred at room tem perature overn igh t, th en cooled to 0 °C, eth yl acetate (0.4 m l,
4.1 m m ol) was added an d th e m ixture was stirred for 15 m in with out coolin g. Th e solution
was th en cooled to –78 °C an d a solution of iodin e (6.3 g, 25 m m ol) in THF was added. Af-
ter stirrin g at room tem perature for 3 h , th e m ixture was poured in to an aqueous solution of
sodium th iosulfate an d extracted with eth er (3×). Th e com bin ed eth ereal extracts were dried
over an h ydrous MgSO4 an d th e solven t was evaporated in vacuum . Ch rom atograph y of th e
crude product on silica (petroleum eth er–eth er–aceton e 8 : 1 : 1) afforded 4 g (69%) of th e
product. 1H NMR (CDCl3): 5.82 s, 2 H (Ar); 5.30 tt, 1 H, J1 = 5.8, J2 = 1.8 (=CH); 4.59 s, 2 H
(CH2N); 4.21 bs, 2 H (CH2OH); 2.16 s, 6 H (CH3). IR (CHCl3): 3 611, 3 451, 2 999, 2 932, 2 667,
1 647, 1 523, 1 443, 1 405, 1 297, 1 050, 1 000. For C10H14INO (291.1) calculated: 41.26% C,
4.85% H, 43.59% I, 4.81% N; foun d: 39.05% C, 4.56% H, 43.51% I, 4.58 N.
(Z)-4-Am in o-3-iodobut-2-en -1-ol (15)
A m ixture of h ydroxylam in e h ydroch loride (0.414 g, 6 m m ol), potassium h ydroxide (0.2 g,
3.5 m m ol), eth an ol (3.3 m l), water (1.2 m l) an d com poun d 14 (0.350 g, 1.2 m m ol) was
h eated un der reflux for 24 h . Th en an oth er portion of potassium h ydroxide (0.1 g, 1.8
m m ol) an d h ydroxylam in e h ydroch loride (0.2 g, 2.9 m m ol) was added an d th e m ixture was
h eated for an oth er 24 h . After coolin g, th e pH of th e reaction m ixture was adjusted to >10
by addition of a dilute solution of sodium h ydroxide, th e solids were filtered off an d th e sol-
ven t was evaporated. Th e residue was dissolved in eth an ol, alum in a (5 g) was added an d
eth an ol was evaporated. Th e dry m ixture was tran sferred on to th e colum n filled with silica
(20 g) an d ch rom atograph y with a m ixture of ch loroform –eth an ol–am m on ium h ydroxide
(75 : 24 : 1) afforded 0.175 g (68%) of th e am in o alcoh ol 15. 1H NMR (DMSO-d6): 6.27 t,
1 H, J = 4.9 (=CH); 3.93 d, J = 4.9 (CH2OH); 3.73 s, 2 H (CH2NH2). IR (KBr): 3 328, 3 278,
2 902, 2 745, 1 654, 1 615, 1 439, 1 322, 1 246, 1 116, 1 077, 1 042, 954, 757. Sin ce n o sat-
isfactory elem en tal an alysis was obtain ed, th e am in e 15 was ch aracterized as sulfate. Th e
am in o alcoh ol was dissolved in m eth an ol an d a solution of sulfuric acid in m eth an ol was
carefully added un til th e m ixture becam e n eutral. Th e sulfate (m .p. 171–175 °C) was precipi-
tated durin g th e n eutralization (its crystallization from acidic solution was un successful).
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450
Havránek, Dvořák:
Addition of a sm all am oun t of eth er aided th e precipitation . 1H NMR (DMSO-d6): 6.17 t, 1 H,
J = 5.2 (=CH); 3.98 d, J = 4.9 (CH2OH); 3.58 d, 2 H, J = 1.1 (CH2NH2). IR (KBr): 3 367, 3 108,
2 882, 1 630, 1 527, 1 477, 1 429, 1 110, 1 010, 880. For C8H18I2N2O6S (524.1): 18.33% C,
3.46% H, 48.43% I, 5.34 % N; foun d: 18.37% C, 3.88% H, 48.13% I, 5.47% N.
(Z)-4-Ben zam ido-1-(ben zoyloxy)-3-iodobut-2-en (16)
an d (Z)-4-Ben zam ido-3-iodobut-2-en -1-ol (17)
A solution of ben zoyl ch loride (1.3 m l, 11 m m ol) in eth er (10 m l) was added dropwise to a
solution of am in o alcoh ol 15 (1.065 g, 5 m m ol) in pyridin e (10 m l) at 0 °C. Th e reaction
m ixture was stirred for 3 h at room tem perature, th en poured in to water, acidified with h y-
droch loric acid un til it becam e sligh tly acidic an d extracted th ree tim es with ch loroform .
Th e organ ic layers were com bin ed, dried over an h ydrous MgSO4 an d ch loroform was evapo-
rated. Crystallization from toluen e afforded 1.602 g (76%) of 16 (m .p. 92 °C). 1H NMR
(CDCl3): 8.02–8.09 m , 2 H (Ar); 7.79–7.85 m , 2 H (Ar); 7.41–7.62 m , 6 H (Ar); 6.46 bs, 1 H
(NH); 6.35 tt, 1 H, J1 = 5.8, J2 = 1.5 (=CH); 4.92 d, J = 5.9 (CH2O); 4.44 dd, 2 H, J1 = 5.9, J2
0.9 (CH2N). IR (CHCl3): 3 452, 3 026, 3 012, 1 719, 1 666, 1 516, 1 486, 1 272, 1 110. For
18H16INO3 (421.2) calculated: 51.32% C, 3.83% H, 30.13% I, 3.33% N; foun d: 51.46% C,
=
C
3.94% H, 30.43% I, 3.29% N.
Alcoh ol 17 was obtain ed by sodium m eth oxide-catalyzed m eth an olysis of 16 at 40 °C
overn igh t. After evaporation of m eth an ol, th e product was separated by ch rom atograph y on
silica (radial ch rom atograph y). Elution with petroleum eth er–eth er–aceton e (50 : 30 : 20) af-
forded 17 as a wh ite solid (m .p. 80–82 °C). 1H NMR (CDCl3): 7.78–7.83 m , 2 H (Ar);
7.42–7.57 m , 3 H (Ar); 6.62 bs, 1 H (NH); 6.22 tt, 1 H, J1 = 5.7, J2 = 1.1 (=CH); 4.36 dd, 2 H,
J1 = 5.9, J2 = 0.9 (CH2NH); 4.22–4.25 m , (CH2OH). Peaks were assign ed accordin g to th e
COSY spectrum . 13C NMR, APT (CDCl3): 168.97, 134.31, 104.00, 67.36, 52.19 (CH2, C);
136.72, 132.74, 129.41, 127.90 (CH3, CH). 13C NMR, n on decoupled: 52.19 dt, Jt = 142.3, Jd
=
4.6. In teraction Jd correspon ds with cis relation of CH2OH an d C-H. IR (CHCl3): 3 608, 3 449,
3 355, 3 011, 1 659, 1 518, 1 487, 1 292, 1 076, 1 004. For C11H12INO2 (317.1) calculated:
41.66% C, 3.81% H, 40.02% I, 4.42% N; foun d: 42.09% C, 3.77% H, 40.41% I, 4.43% N.
(E)-4-Ben zam ido-3-(tributylstan n yl)but-2-en -1-ol (2s)
an d (E)-4-Ben zam ido-2-(tributylstan n yl)but-2-en -1-ol (21)
4-Ben zam idobut-2-yn -1-ol (18; 0.284 g, 1.5 m m ol) an d tetrakis(triph en ylph osph in e)palla-
dium (0.035 g, 0.03 m m ol) were dissolved in an h ydrous THF (7 m l) un der argon an d
tributyltin h ydride (0.37 m l, 1.65 m m ol) was added via syrin ge. After 10 m in , th e solven ts
were evaporated an d th e products were separated by ch rom atograph y (radial ch rom atogra-
ph y). Elution with petroleum eth er–eth er–aceton e 8 : 1 : 1 afforded 0.168 g (23%) of 21 (less
polar) an d 0.192 g (27%) of 2s (m ore polar), respectively.
Compound 21. 1H NMR (CDCl3): 7.75–7.79 m , 2 H (Ar); 7.40–7.53 m , 3 H (Ar); 6.23 s, 1 H
(NH); 5.62 t, 1 H, J = 6.7, 3J(Sn -H,cis) = 66 (=CH); 4.46 d, 2 H, J = 5.3, 3J(Sn -H) = 37
(CH2OH); 4.12 t, 2 H, J = 6.2 (CH2NH); 2.37 t, 1 H, J = 5.3 (OH); 1.25–1.60 m , 12 H
(Sn CH2CH2CH2CH3); 0.82–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3):
168.16, 151.00, 63.94, 39.23, 29.86, 28.09, 10.74 (CH2, C); 135.02, 132.22, 129.29, 127.62
(CH3, CH). IR (CHCl3): 3 618, 3 451, 3 365, 3 010, 2 959, 2 926, 2 872, 2 853, 1 653, 1 579,
1 520, 1 496, 1 462, 1 287, 1 074, 1 026. For C23H39NO2Sn (480.3) calculated: 57.52% C,
8.19% H, 2.92% N; foun d: 57.24% C, 7.88% H, 2.78% N.
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3-(Tributylstannyl)allyl Alcohols
451
Compound 2s. 1H NMR (CDCl3): 7.74–7.80 m , 2 H (Ar); 7.41–7.53 m , 3 H (Ar); 6.32 bs, 1 H
(NH); 6.05 t, 1 H, J = 6.5, 3J(Sn -H,cis) = 65 (=CH); 4.26–4.35 m , 4 H, 3J(Sn -H) = 47 (CH2OH,
CH2NH); 2.78 t, 1 H, J = 5.7 (OH); 1.20–1.60 m , 12 H (Sn CH2CH2CH2CH3); 0.82–1.05 m , 15 H
(Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3): 168.05, 144.73, 134.93, 59.17, 42.70, 29.83,
28.08, 10.46 (CH2, C); 142.87, 132.31, 129.31, 127.53, 14.33 (CH3, CH). IR (CHCl3): 3 613,
3 453, 3 010, 2 959, 2 927, 2 874, 2 853, 1 656, 1 518, 1 485, 1 462, 1 340, 1 074, 1 002. For
C
23H39NO2Sn (480.3) calculated: 57.52% C, 8.19% H, 2.92% N; foun d: 57.56% C, 7.90% H,
2.76% N.
(E)-4-(3-Fluoroben zam ido)-3-(tributylstan n yl)but-2-en -1-ol (2u )
an d (E)-4-(3-Fluoroben zam ido)-2-(tributylstan n yl)but-2-en -1-ol (22)
Th ese stan n an es were prepared as described for com poun ds 2s an d 2l. From a on e m m ol re-
action 0.224 g (45%) of 22 (less polar) an d 0.193 g (38%) of 2u (m ore polar) was obtain ed.
Compound 22. 1H NMR (CDCl3): 7.45–7.53 m , 2 H (Ar); 7.36–7.45 m , 1 H (Ar); 7.15–7.24 m ,
1 H (Ar); 6.26 bs, 1 H (NH); 5.61 t, 1 H, J = 6.6, 3J(Sn -H,cis) = 66 (=CH); 4.47 d, 2 H, J = 5.3,
3J(Sn -H) = 38 (CH2OH); 4.11 t, 2 H, J = 6.1 (CH2NH); 2.20 t, 1 H, J = 5.2 (OH); 1.25–1.62 m ,
12 H (Sn CH2CH2CH2CH3); 0.82–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3):
166.89, 164.70, 162.23, 151.27, 137.47, 63.90, 39.29, 29.84, 28.08, 10.72 (CH2, C); 134.81,
131.02, 123.19, 119.25, 115.10, 14.42 (CH3, CH). IR (CHCl3): 3 617, 3 451, 3 015, 2 958, 2 927,
2 872, 1 659, 1 500, 1 520, 1 482, 1 292, 1 271, 1 023. For C23H38FNO2Sn (498.3) calculated:
55.47% C, 7.69% H, 2.81% N; foun d: 55.46% C, 7.52% H, 2.99% N.
Compound 2n . 1H NMR (CDCl3): 7.45–7.53 m , 2 H (Ar); 7.35–7.45 m , 1 H (Ar); 7.15–7.24 m ,
1 H (Ar); 6.34 bs, 1 H (NH); 6.05 t, 1 H, J = 6.6, 3J(Sn -H,cis) = 66 (=CH); 4.24–4.34 m , 4 H,
3J(Sn -H)
= 48 (CH2OH, CH2NH); 2.62 t, 1 H, J = 5.8 (OH); 1.20–1.65 m , 12 H
(Sn CH2CH2CH2CH3); 0.80–1.05 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3):
166.64, 164.75, 162.29, 144.71, 137.28, 59.18, 42.75, 29.82, 28.07, 10.46 (CH2, C);
142.97, 131.00, 122.96, 119.31, 115.09, 14.32 (CH3, CH). IR (CHCl3): 3 447, 3 363, 3 010,
2 959, 2 927, 2 873, 2 854, 1 658, 1 588, 1 518, 1 482, 1 468, 1 292, 1 271, 1 023, 1 001. For
C
23H38FNO2Sn (498.3) calculated: 55.47% C, 7.69% H, 2.81% N; foun d: 55.53% C, 7.59% H,
2.99% N.
(E)-4-Acetam ido-3-(tributylstan n yl)but-2-en -1-ol (2v)
an d (E)-4-Acetam ido-2-(tributylstan n yl)but-2-en -1-ol (23)
Th ese stan n an es were prepared as described for com poun ds 2s an d 2l. Two m m ol scale reac-
tion afforded 23 (0.282 g, 34%) as a less polar fraction an d 2v (0.219 g, 26%) as a m ore po-
lar fraction after ch rom atograph y on alum in a (50 g) usin g gradien t elution with petroleum
eth er–eth er–aceton e 55 : 40 : 5, 50 : 40 : 10 an d 40 : 40 : 20.
Compound 23. 1H NMR (CDCl3): 5.61 bs, 1 H (NH); 5.501 tt, 1 H, J1 = 6.9, J2 = 1.9,
3J(Sn -H,cis) = 64 (=CH); 4.38 d, 2 H, J = 5.0, 3J(Sn -H) = 38 (CH2OH); 3.89 t, 2 H, J = 6.0
(CH2NH); 2.29 t,
1 H, J = 5.2 (OH); 1.98 s, 3 H (CH3CO); 1.24–1.60 m , 12 H
(Sn CH2CH2CH2CH3); 0.80–1.02 m , 15 H (Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3):
170.76, 150.66, 63.84, 38.89, 29.84, 28.08, 10.71 (CH2, C); 135.04, 24.01, 14.42 (CH3, CH).
IR (CHCl3): 3 450, 3 335, 3 008, 2 959, 2 927, 2 872, 2 854, 1 662, 1 519, 1 463, 1 376, 1 273,
1 021. For C18H37NO2Sn (418.2) calculated: 51.70% C, 8.92% H, 3.35% N; foun d: 51.52% C,
8.43% H, 3.20% N.
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Havránek, Dvořák:
Compound 2v. 1H NMR (CDCl3): 6.58 t, 1 H, J = 6.6, 3J(Sn -H,cis) = 64 (=CH); 5.58 bs, 1 H
(NH); 6.35 t, 2 H, J = 5.8 (CH2OH); 4.06 d, 2 H, J = 5.5, 3J(Sn -H) = 49 (CH2NH); 2.76 t, 1 H, J =
5.5 (OH); 1.96 s, 3 H (CH3CO); 1.24–1.60 m , 12 H (Sn CH2CH2CH2CH3); 0.80–1.02 m , 15 H
(Sn CH2CH2CH2CH3). 13C NMR, APT (CDCl3): 170.81, 144.47, 59.20, 42.28, 29.81, 28.08,
10.43 (CH2, C); 142.71, 24.02, 14.37 (CH3, CH). IR (CHCl3): 3 447, 3 338, 3 008, 2 959, 2 928,
2 872, 2 855, 1 663, 1 517, 1 463, 1 375, 1 279, 1 007. For C18H37NO2Sn (418.2) calculated:
51.70% C, 8.92% H, 3.35% N; foun d: 51.81% C, 8.63% H, 3.23% N.
Solid-Phase Synthesis
Gen eral Meth od for th e Couplin g of Polym er-Attach ed Iodoben zoates with Stan n an es 2
Th e h ydroxy-fun ction alized Ten ta Gel resin was m ixed with iodoben zoic acid (4 equiva-
len ts), diisopropylcarbodiim ide (4 equivalen ts), 1-h ydroxyben zotriazole (4 equivalen ts) an d
4-(dim eth ylam in o)pyridin e (0.4 equivalen ts) in dich lorom eth an e (8 m l/g of resin ) an d th e
m ixture was sh aken for 14 h . Th e polym er was th en filtered off, wash ed with DMF (3×), di-
ch lorom eth an e (3×), aceton e (3×) an d dried un der h igh vacuum . Th e am oun t of attach ed
iodoben zoic acid was 0.25–0.30 m m ol/g of th e polym er (from th e iodin e con ten t).
Th e above iodoben zoic acid attach ed to Ten ta Gel (0.1 g, 0.025–0.03 m m ol), stan n an e 2
(25–30 m g, 0.06–0.09 m m ol) an d 0.5 m l (0.0003 m m ol) of stock solution of palladium cata-
lyst 7 in 1-m eth ylpyrrolidin -2-on e (9 m g of catalyst in 15 m l) were h eated to 110 °C un der
argon for 14 h . Polym er was th an wash ed with DMF (3×), dich lorom eth an e (3×), aceton e
(3×) an d dried un der h igh vacuum .
Tran sform ation of Polym er-Supported Allyl Alcoh ol 3 to Supported Allyl Ch loride 4
Ten ta Gel with attach ed allyl alcoh ol 3 (0.1 g) an d a solution of triph en ylph osph in e in car-
bon tetrach loride–m eth ylen e ch loride (1 m l) were h eated to 35 °C for 14 h . Th e polym er
was th en wash ed with dich lorom eth an e (3×), aceton e (3×) an d dried in h igh vacuum . Th e
solution of triph en ylph osph in e was prepared by dissolvin g of 0.262 g (1 m m ol) triph en yl-
ph osph in e in th e m ixture of carbon tetrach loride (3 m l) an d dich lorom eth an e (4 m l) an d
h eatin g at 35 °C for 0.5 h .
Couplin g of Allyl Ch loride 4 with Stan n an es 2
Ten ta Gel with attach ed allyl ch loride 4 (0.1 g, 0.025–0.03 m m ol), stan n an e 2 (25–30 m g,
0.06–0.09 m m ol) an d 0.5 m l of th e solution of palladium catalyst in 1-m eth yl-
pyrrolidin -2-on e (30 m g of Pd2(dba)3·CHCl3 an d 36 m g of tris(2-tolyl)ph osph in e in 15 m l)
were h eated at 80 °C un der argon for 14 h . Th e polym er was wash ed with DMF (3×), di-
ch lorom eth an e (3×) an d aceton e (3×) an d dried un der h igh vacuum .
Cleavage of Products from th e Polym er Support
Th e substituted Ten ta Gel was stirred at room tem perature in
a solution of sodium
m eth oxide (0.02 m m ol) in a m ixture of m eth an ol (0.5 m l) an d THF (2 m l). After 40 m in ,
th e m ixture was n eutralized with dilute solution of acetic acid in m eth an ol, filtered an d
evaporated.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

3-(Tributylstannyl)allyl Alcohols
453
(Z)-4-Acetamido-2-[4-(methoxycarbonyl)phenyl]but-2-en-1-ol (31a), product of couplin g of
polym er supported 4-iodoben zoate (1) with stan n an e 23 (Table III). 1H NMR (CDCl3):
7.96–8.02 m , 2 H (Ar); 7.53–7.59 m , 2 H (Ar); 6.05 bs, 1 H (NH); 5.83 t, 1 H, J = 7.7 (=CH);
4.58 d, 2 H, J = 6.6 (CH2); 4.09 dd, 2 H, J1 = 6.0, J2 = 7.7 (CH2); 3.91 s, 3 H (OCH3); 1.99 s, 3 H
(CH3CO). HR MS (FAB), for C14H18NO4 (M + 1) calculated: 264.1236; foun d: 264.1259.
(Z)-4-Acetamido-2-[3-(methoxycarbonyl)phenyl]but-2-en-1-ol (31b ), product of couplin g of
polym er supported 3-iodoben zoic acid (28b) with stan n an e 23 (Table III). 1H NMR (CDCl3):
8.13 s, 1 H (Ar); 7.93 d, 1 H, J = 7.7 (Ar); 7.73 d, 1 H, J = 8.2 (Ar); 7.40 t, 1 H, J = 7.7 (Ar);
6.07 bs, 1 H (NH); 5.81 t, 1 H, J = 7.7 (=CH); 4.58 d, 2 H, J = 6.1 (CH2); 4.09 dd, 2 H, J1
6.6, J2 = 7.7 (CH2); 3.91 s, 3 H (OCH3); 1.99 s, 3 H (CH3CO). MS, m/z: 264.1 (M + 1).
=
(Z)-4-Acetamido-2-[2-methyl-5-(methoxycarbonyl)phenyl]but-2-en-1-ol (31c), product of cou-
plin g of polym er supported 3-iodo-4-m eth ylben zoic acid (28c) with stan n an e 23 (Table III).
1H NMR (CDCl3): 7.77–7.86 m , 2 H (Ar); 7.22–7.32 m , 1 H (Ar); 5.95 s, 1 H (NH); 5.40 t, 1 H,
J = 8.0 (=CH); 4.43 d, 2 H, J = 6.0 (CH2); 4.11 t, 2 H, J = 6.9 (CH2); 3.89 s, 3 H (OCH3); 2.32 s,
3 H (CH3); 2.02 s, 3 H (CH3). MS, m/z: 278.1 (M + 1).
(Z)-4-Acetamido-2-{4-[N-(tert-butyloxycarbonyl)amino]-3-(methoxycarbonyl)phenyl}but-2-en-1-ol
(3 1 d ), p rod u ct of cou p lin g of p olym er su p p orted 2-[N-(tert-butyloxycarbon yl)am in o]-
5-iodoben zoic acid (28d ) with stan n an e 23 (Table III). 1H NMR (CDCl3): 10.26 s, 1 H
(Boc-NH); 8.38 d, 1 H, J = 8.8 (Ar); 8.18 d, 1 H, J = 2.8 (Ar); 7.60 dd, 1 H, J1 = 8.8, J2 = 2.2 (Ar);
6.01 s, 1 H (NH); 5.74 t, 1 H, J = 7.8 (=CH); 4.55 d, 2 H, J = 6.6 (CH2); 4.07 dd, 2 H, J1 = 6.6,
J2 = 8.2 (CH2); 3.91 s, 3 H (OCH3); 1.52 s, 9 H ((CH3)3C). MS, m/z: 379.1 (M + 1).
Triene 27. 1H NMR (CDCl3): 7.95–8.03 m , 2 H (Ar); 7.23–7.47 m , 2 H (Ar); 5.80–5.88 m ,
1 H (=CH); 5.33–5.53 m , 1 H (=CH); 4.95–5.20 m , 1 H (=CH); 4.16 bs, 2 H (CH2OH); 3.92 m ,
3 H (OCH3); 2.98–3.01 m , 4 H (=CH-CH2-CH=); 1.70–2.11 m , 9 H (=C-CH3). MS, m/z: 314
(M + 1).
We thank the Trega Bioscience (San Diego, U.S.A.) for financial support of this project and Dr M.
Lebl for helpful discussion.
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