Synthesis of functionalized deuterioallylic compounds

Article abstract of DOI:10.1021/jo982396r

Functionalized deuterioallylic compounds were efficiently prepared by reaction of the corresponding propargylic derivative with the Schwartz reagent followed by hydrolysis of the adduct with D₂O. The Z-3-deuterio-2- propenylstannane, prepared i

Full text of DOI:10.1021/jo982396r

J . Org. Chem. 1999, 64, 3563-3566
3563
Syn th esis of F u n ction a lized Deu ter ioa llylic Com p ou n d s
David Orain and J ean-Claude Guillemin*
Laboratoire de Synthe`ses et Activations de Biomole´cules, ESA 6052, ENSCR, Avenue du Ge´ne´ral Leclerc,
35700 Rennes, France
Received December 8, 1998
Functionalized deuterioallylic compounds were efficiently prepared by reaction of the corresponding
propargylic derivative with the Schwartz reagent followed by hydrolysis of the adduct with D2O.
The Z-3-deuterio-2-propenylstannane, prepared in pure form for the first time, is a useful reagent
for the preparation of deuterioallylic compounds which cannot be synthesized by hydrozirconation
of the corresponding derivatives.
In tr od u ction
rhydride.7 Most of these approaches can be extended to
the deuterio derivatives Cp2ZrDCl 2 and Cp2ZrDCl 2′.8
The addition of Cp2ZrHCl 1 on propargyl bromide 3 in
a halogenated solvent followed by the addition of D2O
(method A) led to the (E)-1-deuterio-3-bromopropene 4a
in a 83% yield and with an isotopic purity higher than
97%. The product was easily isolated when 1,1,2,2-
tetrachloroethane was used as solvent. Allyl bromide 4a
diluted in THF has also been prepared by the in situ
generation of the zirconium hydride 1′ (method B)
(yield: 86%, isot. pur. ≈ 94%). To prepare the (E)-1,2-
dideuterio derivative 4b diluted in THF, a similar reac-
tion has been performed using compound 2′ as reagent
(Scheme 1).
Although the chemistry of functionalized allylic com-
pounds is one of the most efficient ways to form carbon-
carbon bonds,1 the synthesis of selectively labeled allylic
derivatives bearing functionalized groups is still an
interesting challenge. Such compounds are potential
useful reagents to prepare other selectively labeled
species or to precise the reactions pathways of reactions
both with and without an allylic transposition.1 Deute-
rioallylic alcohols are easily formed by reduction of the
corresponding acrylaldehyde or acrylic esters,2 no isomer-
ization occurring even in the presence of strong Lewis
bases. However, starting from these alcohols, approaches
involving substitution reactions only led to mixtures of
isomers of the expected product. These results were
attributed to a low regioselectivity of the reaction or to
the isomerization of the formed product.3,4 The reduction
of propargylic compounds is another general approach
to the corresponding allylic systems,5 but the presence
of functional groups strongly limits the choice of the
reducing agent. We now report an approach using as
reagent the biscyclopentadienylchlorozirconium hydride
1 (the Schwartz reagent) followed by hydrolysis of the
formed adduct by D2O. The role played by the nature of
the functional group of the alkynyl derivatives is clearly
evidenced. Also described is the efficacy of the formed
deuterioallylstannane in the preparation of deuterioal-
lylic compounds which cannot be prepared by the hy-
drozirconation approach.
Starting from the (tert-butyldimethylsiloxy)prop-2-yn-
1-ol 5 and the hydride 1′, the (E)-(tert-butyldimethylsi-
loxy)-3-deuterio-2-propene 6a was prepared in a 65%
yield and with an isotopic purity higher than 96%
(Scheme 1). The corresponding (E)-2,3-dideuterioderiva-
tive 6b was prepared from compounds 5, 2′, and D2O in
a 64% yield (isot. pur. > 95%).9
Similarly, the propargyldimethylphenylsilane 7 reacted
with Cp2ZrHCl (1 or 1′) to give the corresponding adduct.
The latter led to the E-deuterioallylsilane 8a after
addition of D2O (yield: 93%, isot. pur. > 96%).10 Using
2′, then D2O, the (E)-2,3-dideuteriopropenylsilane 8b was
obtained in a 95% yield (isot. pur. > 95%) (Scheme 1).
However the Schwartz reagent is not efficient with
some functional groups. So, the propargylphosphonic acid
diethyl ester 9 reacted with a stoichiometric or substo-
ichiometric amount of the Schwartz reagent 1 to give,
after hydrolysis, the corresponding 1-propynylphosphonic
acid diethyl ester 10 in a good yield (82%) and only traces
of the expected product, the 3-deuterio-2-propenylphos-
Resu lts a n d Discu ssion
Several preparations of the Schwartz reagent have
been reported.6 A quite similar compound (1′) can be
generated in situ starting from Cp2ZrCl2 and the supe-
(6) Wailes, P. C.; Weigold, H. J . Organomet. Chem. 1970, 24, 405-
411. Carr, D. B.; Schwartz, J . J . Am. Chem. Soc. 1979, 101, 3521-
3531. Buchwald, S. L.; LaMaire, S. J .; Nielsen, R. B.; Watson, B. T.;
King, S. M. Tetrahedron Lett. 1987, 28, 3895-3898. Buchwald, S. L.;
La Maire, S. J .; Nielsen, R. B.; Watson, B. T.; King, S. M. Org. Synth.
1993, 71, 77-81. For a review on hydrozirconation see: Wipf, P.; J ahn,
H. Tetrahedron Rep. 1996, 52, 12853-12910.
(1) Yamamoto, Y.; Asao, N.Chem. Rev. 1993, 93, 2207-2293.
(2) See for example: Casey, C. P.; Vosejpka, P. C.; Underiner, T.
L.; Slough, G. A.; Gavney, J . A., J r. J . Am. Chem. Soc. 1993, 115, 6680-
6688. Legoupy, S.; Cre´visy, C.; Guillemin, J .-C.; Gre´e, R.; Toupet, L.
Chem.sEur. J . 1998, 4, 2155-2165.
(3) See for example: (a) Pasto, D. J .; Huang, N.-Z. J . Org. Chem.
1986, 51, 412-413. (b) Mazzanti, G.; Ruinaard, R.; Van Vliet, L. A.;
Zani, P.; Bonini, B. F.; Zwanenburg, B. Tetrahedron Lett. 1992, 33,
6383-6386. (c) Hill, E. A.; Boyd, W. A.; Desai, H.; Darki, A.; Bivens,
L. J . Organomet. Chem. 1996, 514, 1-11. (d) Capps, S. M.; Lloyd-J ones,
G. C.; Murray, M.; Peakman, T. M.; Walsh, K. E. Tetrahedron Lett.
1998, 39, 2853-2856.
(7) Lipshutz, B. H.; Keil, R.; Ellsworth, E. L. Tetrahedron Lett. 1990,
31, 7257-7260.
(8) Zippi, E. M.; Andres, H.; Morimoto, H.; Williams, P. G. Synth.
Commun. 1994, 24, 1037-1044.
(9) The preparation of a (Z)-deuteriosiloxypropene has recently been
reported. Ridgway, B. H.; Woerpel, K. A. J . Org. Chem. 1998, 63, 458-
460.
(10) The preparation of mixtures of (E) and (Z) isomers has already
been reported. Fleming, I.; Langley, J . A. J . Chem. Soc., Perkin Trans.
1 1981, 1421-1423.
(4) Cadiot, P.; Matarasso-Tchiroukine, E. C. R. Acad. Sci. C 1972,
274, 2118-2120.
(5) See for example: McMichael, K. D. J . Am. Chem. Soc. 1967, 89,
2943-2947.
10.1021/jo982396r CCC: $18.00 © 1999 American Chemical Society
Published on Web 04/24/1999

3564 J . Org. Chem., Vol. 64, No. 10, 1999
Orain and Guillemin
Sch em e 1
Sch em e 3
Sch em e 2
riopropargyltriphenylstannane 14b13 and the Schwartz
reagent 1. After hydrolysis with H2O, the (Z)-3-deuterio-
propenyltriphenylstannane 13b was obtained in a 95%
yield and with a high isotopic purity (>97%). The 3,3-
dideuteriopropenyltriphenylstannane 13e was also pre-
pared by this approach using D2O in the hydrolysis step
but with an isotopic purity never better than 80%
(Scheme 3).
phonate 11 (Scheme 2). Compound 1 thus promoted the
isomerization of propargylphosphonate 9 in the propynyl
isomer 10. This property was confirmed by the formation
of phosphonate 10 starting from the allenylphosphonic
acid diethyl ester 12 and small amounts of the Schwartz
reagent 1.
Stannane 13b is a very useful reagent for mechanistic
studies and synthetic applications. It can be used to
prepare various labeled allylic derivatives which cannot
be synthesized via the approach reported above. Its
addition to a weak, medium, or strong Lewis acid clearly
showed the ability of such compounds to rearrange from
one isomer to the other one: with a weak Lewis acid such
as PBr3 or AsCl3 diluted in CDCl3, only the kinetic
products, the phosphane 15 (a potential precursor of an
isomer of the deuterioallylphosphonate 11) and the
arsane 16a , respectively, were isolated even when the
reaction was performed at room temperature.14 Arsane
16a diluted in CDCl3 very slowly rearranged at RT to
give after some days a mixture of the isomers 16a and
(Z)- and (E)-16b. With tin tetrabromide (a moderatly
strong Lewis acid) diluted in CDCl3, only the kinetic
product 17a was observed by low temperature (-50 °C)
NMR, while a mixture of isomers 17a and (Z)- and (E)-
17b was obtained at RT. At a temperature higher than
-80 °C, the allyltrichlorostannane 18a diluted in CD2-
Cl2 rearranged in a mixture of isomers 18a and (Z)- and
(E)-18b. With SbCl3, a complex mixture containing the
isomers 19a and (Z)- and (E)-19b probably in a thermo-
dynamic equilibrium was observed even when the reac-
tion was performed and analyzed at -80 °C (Scheme 4).14
Allylstannanes are also very useful reagents in the
preparation of homoallylic alcohols or amines.1,15 It is
well-known that the reaction pathway of the allylation
of an electrophile by an allylic stannane in the presence
Some approaches have already been reported to pre-
pare deuterioallylstannanes but have been limited by
partial isomerization in the reaction mixture before
isolation.4 Using the Schwartz reagent and a propargyl-
stannane, a selective hydrolysis of the Zr-C bond of the
adduct should be easily performed, while the experimen-
tal conditions used with some other reagents (as boranes
or stannanes for example) probably cannot prevent a
partial or complete loss of the tin group in the allylic
position.11 However, starting from propargyltriphenyl-
stannane 14a 12 and Cp2ZrHCl 1′ generated in situ, only
a mixture of three isomers, 13a -c, was obtained in a
1:1:2 ratio (Scheme 3). Using pure Schwartz reagent 1
and stannane 14a , the subsequent addition of D2O led
to the 3-deuterio-2-propenyltriphenylstannane 13a in a
95% yield, but the isotopic purity only rose to 86%. The
presence of about 14% (or more) of the hydrogenated
stannane 13d cannot be avoided and is dependent on the
presence of traces of impurities in the Schwartz reagent.
The presence of the isomer 13c has been excluded on the
basis of the NMR spectra. Moreover we never observed
any isomerization of stannane 13a even after 2 h of
stirring at RT in the presence of small amounts of
compound 1 with or without water.
To prepare a pure sample of a deuterioallylstannane,
a better approach was found starting from the 3-deute-
(12) Le Quan, M.; Cadiot, P. Bull. Soc. Chim. Fr. 1965, 45-47.
(13) The 1-deuteriopropargylbromide was prepared as reported.
Ollis, W. D.; Sutherland, I. O.; Thebtaranonth, Y. J . Chem. Soc., Perkin
Trans. 1 1981, 1981-1993. Compound 14b was prepared starting from
1-deuteriopropargylbromide with the experimental procedure reported
for 14a (ref 12).
(14) Le Serre, S.; Guillemin, J .-C.; Karpati, T.; Soos, L.; Nyula´szi,
L.; Veszpre´mi, T. J . Org. Chem. 1998, 63, 59.
(15) Tin in Organic Synthesis; Pereyre, M., Quintard, J .-P., Rahm,
A., Ed.; Butterworth & Co. (Publishers Ltd.): London, 1987; pp 130-
256.
(11) . For a recent review on boron derivatives in organic chemistry
see: Vaultier, M.; Carboni, B. Boron. In Comprehensive Organometallic
Chemistry II, Vol. 11; Elsevier Science Ltd.: New York, 1995; Chapter
5, pp 191-276. Selective monodestannylation of distannane derivatives
has already been reported for symmetric compounds: Bogoradovskii,
E. T.; Cherkasov, V. N.; Zavgorodnii, V. S.; Rogozev, B. I.; Petrov, A.
A. J . Gen. Chem. USSR 1980, 50, 1641-1649. Guillemin, J . C.;
Lassalle, L.; Dre´an, P.; Wlodarczak, G.; Demaison, J . J . Am. Chem.
Soc. 1994, 116, 8930-8936.

Functionalized Deuterioallylic Compounds
J . Org. Chem., Vol. 64, No. 10, 1999 3565
oxide (99.992%) were purchased from Aldrich and used as
received. Lithium triethylborodeuteride (Super-Deuteride) was
purchased from Fluka. The Schwartz reagent 1 and biscyclo-
pentadienylzirconium dichloride were purchased from Strem.
The isotopic purity was determined by 1H and 13C NMR
spectroscopy. The prop-2-ynyltriphenylstannane 14a 12 and the
1-deuteriopropargylbromide13 have been prepared as reported.
Gen er a l P r oced u r e for Hyd r ozir con a tion Rea ction
Usin g P u r e Sch w a r tz Rea gen t 1 (Meth od A). In a dried
Schlenck flask equipped with a stirring bar were introduced
under argon the Schwartz reagent 1 (258 mg, 1 mmol) and
THF (5 mL). The propargylic derivative (0.8 equiv) was then
added, and the mixture was stirred at RT for 1 h. Pure D2O
(500 µL) was quickly added, and the mixture was stirred for
10 min. Diethyl ether (10 mL) was added, and the mixture
was dried on MgSO4. The product was purified by chromatog-
raphy on alumina except compound 4a , which was prepared
in 1,1,2,2-tetrachloroethane and purified by trap-to-trap distil-
lation.
Sch em e 4
Sch em e 5
Gen er a l P r oced u r e for Hyd r ozir con a tion Rea ction
Usin g th e Sch w a r tz Rea gen t Gen er a ted in Situ (Meth od
B). In a dried Schlenck flask protected from the light by
aluminum foil and equipped with a stirring bar were intro-
duced under argon Cp2ZrCl2 (292 mg, 1 mmol) and THF (10
mL). LiEt3BH or LiEt3BD (1 equiv) was then slowly added,
and the mixture was stirred for 45 min at RT. The propargylic
derivative (1 equiv) was added, and the stirring was main-
tained for 1 h. Pure D2O (500 µL) was quickly added, and the
mixture was stirred for 30 min. Diethyl ether (10 mL) was
added, and the mixture was dried on MgSO4. The product was
purified by chromatography on alumina. Compounds 8a and
8b have been prepared on gram-scale by this approach.
(E)-3-Br om o-1-d eu ter iop r op -1-en e 4a . Yield: 83%, isot.
pur. > 97% (method A); 86% (crude), isot. pur. ≈ 94% (method
of a Lewis acid is dependent on this Lewis acid.1,16 Thus,
using BF3-Et2O as Lewis acid, stannane 13b, and
benzaldehyde, the reaction occurred at -78 °C without
transmetalation17 and mainly led to only one kind of
regioisomer of the corresponding homoallylic alcohol, the
syn-and anti-2-deuterio-1-phenylbut-3-en-1-ol 20a (Scheme
5). The presence of syn and anti isomers has been
evidenced by 2H NMR spectroscopy. A 4:1 ratio has been
observed and the structure of the major isomer, formed
from the Z-derivative 13b, is probably the syn compound
by analogy with crotyl derivatives.1 Using SbCl3 as Lewis
acid,14 the isomers 20b and 20a were obtained in a 5:1
ratio when the reaction was performed at -78 °C. In this
case, a redistribution reaction between stannane 13b and
SbCl3 occurred and was quickly followed by the addition
of the formed stibine 19a on the electrophile before
equilibrium between both isomers 19a and 19b. The
reaction performed at -50 °C gave isomers 20a and 20b
in a 6:4 ratio, showing that, at this temperature, the
isomerization occurs faster than the allylation reaction
of the electrophile. In these experiments using SbCl3 as
Lewis acid, the observed 1:1/syn:anti ratio is consistent
with a reaction pathway involving a transmetalation
reaction.14,17 Competitions between isomerization and
allylation have already been reported and are generally
a consequence of some steric hindrance or complexation.18
To our knowledge, this is the first example with deute-
rioallyl derivatives.
1
B). H NMR (400 MHz, CDCl3) δ 6.01 (dtt, 1H, J ) 15.6, 7.6,
1.4 (3J HDcis) Hz); 5.28 (d, 1H, J ) 15.6 Hz); 3.92 (dd, 2H, J )
7.6, 0.9 Hz). 13C NMR (100 MHz, CDCl3) δ 134.0; 118.8 (1J CD
) 24.0 Hz (t)), 32.7.
(E)-3-Br om o-1,2-d id eu ter iop r op -1-en e 4b. Yield: 86%,
isot. pur. > 94% (method B). 1H NMR (400 MHz, CDCl3) δ:
5.28 (s, 1H); 3.92 (d, 2H, J ) 0.9 Hz). 13C NMR (100 MHz,
CDCl3) δ: 134.0; 118.8 (1J CD ) 24.1 Hz (t)), 32.7.
(E )-1-(t er t -Bu t yld im e t h ylsiloxy)-3-d e u t e r iop r op -2-
en e 6a . Yield: 65%, isot. pur. > 96% (method B). 1H NMR
(400 MHz, CDCl3) δ: 5.93 (dtt, 1H, J ) 16.8, 4.7, 1.5 (3J HDcis
)
Hz); 5.25 (dt, 1H, J ) 16.8, 2.0 Hz); 4.18 (dd, 2H, J ) 4.7, 2.0
Hz); 0.91 (s, 9H); 0.07 (s, 6H). 13C NMR (100 MHz, CDCl3) δ:
137.2, 113.6 (1J CD ) 23.9 Hz (t)), 64.0, 25.6, 18.3, -5.3. HRMS
calcd for C9H19DOSi: 173.1349. Found: 173.134.
(E)-1-(ter t-Bu tyld im eth ylsiloxy)-2,3-d id eu ter iop r op -2-
en e 6b. Yield: 64%, isot. pur. > 95% (method B). 1H NMR
2
(400 MHz, CDCl3) δ: 5.26 (t, 1H, J HD ) 1.5 Hz, dCHD); 4.19
(s, 2H); 0.93 (s, 9H); 0.09 (s, 6H). 13C NMR (100 MHz, CDCl3)
δ: 137.1 (1J CD ) 24.4 Hz (t)), 113.3 (1J CD ) 24.3 Hz (t)), 67.7,
25.6, 18.1, -5.4.
(E)-3-(Dim eth ylp h en ylsilyl)-1-d eu ter iop r op -1-en e 8a .
1
Yield: 93%, isot. pur. > 96% (method B). H NMR (400 MHz,
In conclusion, we have reported several efficient ap-
proaches to selectively prepare functionalized deuterio-
allylic derivatives. The Schwartz reagent is useful to
synthesize such products in one step or via a reagent as
an allylstannane.
CDCl3) δ: 7.6 (m, 2H); 7.4 (m, 3H); 5.84 (dtt, 1H, J ) 16.8,
8.2, 1.5 (3J HDcis) Hz); 4.96 (dt, 1H, J ) 16.8, 1.5 Hz); 1.86 (dd,
2H, J ) 8.2 Hz, 1.5 Hz); 0.40 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ: 138.6, 134.4, 133.6, 128.8, 127.7, 113.1 (1J CD ) 24.2
Hz (t)), 23.6, -3.5. HRMS calcd for C11H15DSi: 177.1084.
Found: 177.111.
(E )-3-(Dim e t h ylp h e n ylsilyl)-1,2-d id e u t e r iop r op -1-
en e 8b. Yield: 95%, isot. pur. > 95% (method B). 1H NMR
(400 MHz, CDCl3) δ: 7.6 (m, 2H); 7.4 (m, 3H); 4.93 (s, 1H);
1.84 (s, 2H); 0.37 (s, 6H). 13C NMR (100 MHz, CDCl3) δ: 138.6,
133.6 (1J CD ) 23.2 Hz), 129.0, 127.7, 113.0 (1J CD ) 24.1 Hz),
23.5, -3.5. HRMS calcd for C11H14D2Si: 178.1147. Found:
178.115.
Exp er im en ta l Section
Gen er a l P r oced u r es. All manipulations were performed
under an atmosphere of dry argon. Lithium triethylborohy-
dride (Super-Hydride), Schwartz reagent 2, and deuterium
(16) Le Serre, S.; Guillemin, J .-C. Organometallics 1997, 16, 5844-
5849.
(E)-3-Deu ter iop r op -2-en ylp h osp h on ic Acid Dim eth yl
(17) Denmark, S. E.; Wilson, T.; Willson, T. M. J . Am. Chem. Soc.
1988, 110, 984-986.
(18) Depew, K. M.; Danishefsky, S. J .; Rosen, N.; Sepp-Lorenzino,
L. J . Am. Chem. Soc. 1996, 118, 12463-12464. Hoffman, R. W.;
Polachowski, A. Chem.sEur. J . 1998, 4, 1724-1730.
1
Ester 11. Yield ≈ 4% (crude). H NMR (400 MHz, CDCl3) δ:
5.80 (dtd, 1H, J ) 17.0, 7.3, 1.2 Hz); 5.24 (dtd, 1H, J ) 17.0,
4.9, 1.5 Hz); 3.76 (d, 6H, J ) 12.0 Hz); 2.64 (ddd, 2H, J ) 22.1,
7.3, 1.2 Hz). 31P NMR (121 MHz, CDCl3) δ: 26.1.

3566 J . Org. Chem., Vol. 64, No. 10, 1999
Orain and Guillemin
3-Deu ter io-2-p r op yn yltr ip h en ylsta n n a n e 14b. In a 250
mL three-necked flask equipped with a nitrogen inlet, a reflux
condenser, and a stirring bar were introduced magnesium (1.2
g, 50 mmol) and diethyl ether (10 mL). A few drops of
1-deuteriopropargylbromide13 were added, and the reaction
was initiated by addition of few milligrams of HgCl2. The
1-deuteriopropargylbromide (6.0 g, 50 mmol) diluted in diethyl
ether (50 mL) was then added at a rate to maintain the reflux
of the solvent. At the end of the addition, the mixture was
stirred for 15 min, and the chlorotriphenylstannane (18 g, 46
mmol) diluted in THF (30 mL) was added. After 2 h of stirring
under reflux, the cooled solution was poured in a saturated
ammonium chloride solution. The reaction mixture was ex-
tracted with diethyl ether (2 × 50 mL), and the combined
organic layers were dried over anhydrous MgSO4. After
removal of solvents in vacuo, crystallization in hexanes gave
the 3-deuterioprop-2-ynyltriphenylstannane 14b (9.5 g) in a
53% yield. Isot. pur. > 97%. 1H NMR (400 MHz, CDCl3) δ:
7.76 (m, 6H); 7.52 (m, 9H); 2.37 (s, 2H, J SnH ) 63.0 Hz). 13C
NMR (100 MHz, CDCl3) δ: 137.3, 136.8, 129.3; 128.3, 82.6 (J CD
) 7.7 Hz); 67.6 (J CD ) 37.9 Hz); -1.8 (J SnC ) 324 Hz (d)).
1H, J ) 17.5, 6.5, 1.2 Hz). 31P NMR (121 MHz, CDCl3) δ: 177.1.
13C NMR (100 MHz, CDCl3) δ: 46.3 (1J CD ) 20.9 Hz (t)), 121.7,
129.1. HRMS m/z calcd for C3H4Br2DP: 230.8559. Found:
230.855.
1-Deu ter iop r op -2-en yld ich lor oa r sa n e 16a . Yield: 86%.
Isot. pur. > 96%. 1H NMR (400 MHz, CDCl3) δ: 5.90 (ddd,
1H, J ) 16.9, 10.2, 7.9 Hz); 5.30 (dd, 1H, J ) 10.2, 1.2 Hz);
5.26 (dd, 1H, J ) 16.9, 1.2 Hz); 3.19 (dt, 2H, J ) 7.9, 1.1 Hz).
13C NMR (100 MHz, CDCl3) δ: 128.0, 121.6, 48.4 (1J CD ) 21.6
Hz (t)). HRMS calcd for C3H4AsCl2D: 186.9048. Found:
186.905.
1-Deu t er iop r op -2-en ylt r ib r om ost a n n a n e 17a . Yield
(crude): 73%. Isot. pur. > 95%. 1H NMR (400 MHz, CDCl3,
-50 °C) δ: 5.97 (ddd, 1H, J ) 16.3, 9.7, 7.9 Hz); 5.48 (d, 1H,
J ) 16.3 Hz); 5.45 (d, 1H, J ) 9.7 Hz); 3.32 (dt, 1H, J ) 7.9
Hz, J SnH ) 112.3 Hz (d)). 13C NMR (100 MHz, CDCl3, -50 °C)
δ: 128.3, 121.3, 37.8 (1J CD ) 21.9 Hz (t)). 119Sn NMR (112 MHz,
CDCl3) δ -171.2.
1-Deu t er iop r op -2-en ylt r ich lor ost a n n a n e 18a . Yield
1
(crude): 70%. Isot. pur. > 93%. H NMR (400 MHz, CD2Cl2,
-80 °C) δ: 5.97 (ddd, 1H, J ) 16.8, 10.0, 8.2 Hz); 5.45 (d, 1H,
J ) 16.8 Hz); 5.38 (d, 1H, J ) 10.0 Hz); 3.26 (brd t, 1H, J )
8.2 Hz, J SnH ) 125.8 Hz (d)). 13C NMR (100 MHz, CD2Cl2, -80
°C) δ: 127.6, 121.7, 37.2 (1J CD ) 22.0 Hz (t)). 119Sn NMR (112
MHz, CDCl3) δ: -25.7.
4
119Sn NMR (112 MHz, CDCl3) δ: -121.7 (t, J SnD ) 6.6 Hz).
Anal. Calcd for C21H17DSn: C, 64.60; H, 4.91. Found: C, 64.36;
H, 4.96. HRMS (LSIMS with cesium gun, positive mode,
matrix: mNBA) m/z: calcd for
390.0415; found 390.042.
C
21H16D120Sn [M - H]+
Rea ction of Sta n n a n e 13d w ith Ben za ld eh yd e in th e
P r esen ce of a Lew is Acid . Gen er a l P r oced u r e. In a dried
two-necked flask equipped with a stirring bar and a nitrogen
inlet were introduced benzaldehyde (76 µL, 0.75 mmol) and
CH2Cl2 (6 mL). The solution was cooled to -78 °C and the
Lewis acid (1.2 mmol) was added. After 15 min of stirring,
stannane 13b (390 mg, 1 mmol) diluted in CH2Cl2 (3 mL) was
slowly added, and the solution was stirred for 3 h at -78 °C.
The mixture was then poured in a saturated solution of NH4-
Cl. After a usual workup, the alcohol 20 was purified by
chromatography on silica gel (diethyl ether/petroleum ether
1:9).
2-Deu ter io-1-p h en ylbu t-3-en -1-ol 20a . BF3-Et2O was
used as Lewis acid. Yield: 64%. Isot. pur. > 92%. 1H NMR
(400 MHz, CDCl3) δ: 7.29 (m, 5H); 5.63 (ddd, 1H, J ) 17.3,
9.7, 7.2 Hz); 5.11 (dd, 1H, J ) 17.3, 1.5 Hz), 5.07 (dd, 1H, J )
9.7, 1.5 Hz), 4.52 (d, 1H, J ) 7.6 Hz), 2.85 (s, 1H), 2.30 (dd,
1H, J ) 7.6, 7.2 Hz). 13C NMR (100 MHz, CDCl3) δ: 141.5,
135.1, 128.8, 127.9, 126.3, 118.9, 73.7, 44.0 (1J CD ) 20.2 Hz
(t)).
(E)-3-Deu ter iop r op -2-en yltr ip h en ylsta n n a n e 13a . This
compound was prepared starting from prop-2-ynyltriphenyl-
stannane 14a (method A). Yield: 90%. Isot. pur. e 86%. 1H
NMR (400 MHz, CDCl3) δ: 7.60 (m, 6H); 7.41 (m, 9H); 6.10
(m, 1H); 4.97 (d, 1H, J ) 16.8 Hz); 2.45 (d, 2H, J ) 7.1 Hz).
13C NMR (100 MHz, CDCl3) δ: 139.0, 137.7, 137.6, 129.7,
129.2, 112.8 (1J CD ) 23.9 Hz (t)), 18.4 (3J CD ) 2.0 Hz (t)). 119Sn
NMR (112 MHz, CDCl3) δ: -120.7.
(Z)-3-Deu ter iop r op -2-en yltr ip h en ylsta n n a n e 13b. This
compound was prepared starting from 3-deuterioprop-2-ynyl-
triphenylstannane 14b (method A with H2O). Yield: 95%, isot.
pur. > 97%. 1H NMR (400 MHz, CDCl3) δ: 7.6 (m, 6H); 7.3
(m, 9H); 6.10 (brd dt, 1H, J ) 9.9, 8.4 Hz); 4.82 (d, 1H, J ) 9.9
Hz); 2.45 (d, 2H, J ) 8.4 Hz). 13C NMR (100 MHz, CDCl3) δ:
138.3, 137.0, 135.7, 129.0, 128.4, 112.1 (1J CD ) 23.5 Hz (t)),
17.7. 119Sn NMR (112 MHz, CDCl3) δ: -120.7 (4J SnD ) 3.0 Hz).
Anal. Calcd for C21H19DSn: C, 64.27; H, 5.40. Found: C, 64.48;
H, 5.27. HRMS (LSIMS with cesium gun, positive mode,
matrix: mNBA) m/z: calcd for
392.0572; found 392.057.
C
21H18D120Sn [M - H]+
4-Deu ter io-1-p h en ylbu t-3-en -1-ol 20b. SbCl3 was used as
Lewis acid. Yield: 78%. Isot. pur. > 81%. Z:E/45:55. (Z) 1H
NMR (400 MHz, CDCl3) δ: 7.29 (m, 5H); 5.73 (dt, 1H, J )
8.3, 7.2 Hz); 5.07 (d, 1H, J ) 8.3 Hz), 4.62 (d, 1H, J ) 6.6 Hz),
4.52 (s, 1H), 2.45 (ddt, 1H, J ) 7.2, 6.6 Hz). 13C NMR (100
MHz, CDCl3) δ: 141.5, 135.1, 128.8, 127.9, 126.3, 118.8 (1J CD
3,3-Did eu ter iop r op -2-en yltr ip h en ylsta n n a n e 13e. This
compound was prepared starting from 3-deuterioprop-2-ynyl-
triphenylstannane 14b and D2O (method A). Yield: 80%. Isot.
1
pur. e 80%. H NMR (400 MHz, CDCl3) δ: 7.60 (m, 6H); 7.41
(m, 9H); 6.10 (t, 1H, J ) 7.1 Hz); 2.45 (d, 2H, J ) 7.1 Hz). 13C
NMR (100 MHz, CDCl3) δ: 139.0, 137.7, 137.6, 129.7, 129.2,
112.8, 18.4. 119Sn NMR (112 MHz, CDCl3) δ: -120.7.
1
) 23.7 Hz (t)), 44.1. (E) H NMR (400 MHz, CDCl3) δ: 7.29
(m, 5H); 5.73 (ddt, 1H, J ) 17.8, 7.2 Hz); 5.11 (d, 1H, J ) 17.8
Hz), 4.62 (d, 1H, J ) 6.6 Hz), 4.52 (s, 1H), 2.45 (dd, 1H, J )
7.1, 6.6 Hz). 13C NMR (100 MHz, CDCl3) δ: 141.5, 135.1, 128.8,
127.9, 126.3, 118.8 (1J CD ) 23.7 Hz (t)), 44.1.
Rea ction of Sta n n a n e 13d w ith Lew is Acid s P Br 3,
AsCl3, Sn Br 4, a n d Sn Cl4. The reaction was performed in an
NMR tube at low temperature. The stannane 13b (0.5 mmol)
diluted in CD2Cl2 or CDCl3 (300 µL) was slowly added to the
Lewis acid (1 equiv) diluted in the same solvent (300 µL) and
cooled to -80 °C (SnCl4), -50 °C (SnBr4), -20 °C (AsCl3), or
RT (PBr3). The NMR tube was shaken for a few seconds and
directly introduced in the cooled NMR probe. Phosphane 15
and arsane 16a have also been prepared on gram-scale in CH2-
Cl2 and purified by trap-to-trap distillation in vacuo.14
1-Deu t er iop r op -2-en yld ib r om op h osp h a n e 15. Yield:
63%. Isot. pur. > 97%. 1H NMR (400 MHz, CDCl3) δ: 5.89
(dddd, 1H, J ) 19.8, 10.1, 6.5, 4.3 Hz); 5.38 (ddm, 1H, J )
10.2, 4.1 Hz); 5.33 (ddt, 1H, J ) 19.8, 4.1, 1.2 Hz); 3.48 (ddt,
Su p p or tin g In for m a tion Ava ila ble: 400-MHz 1H and
100-MHz 13C NMR spectral data of arsanes 16b,c, stannanes
17b,c, 18b,c. 400-MHz 1H, 100-MHz 13C, and 121-MHz 31P
NMR spectra of the phosphane 15. 400-MHz 1H and 100-MHz
13C spectra of 6a ,b, 8a ,b, 13b, 14b, 16a , 17a , 18a , 20b and
1
mixtures of isomers 16a -c, 17a -c, 18a -c. 400-MHz H, 46
MHz 2D, and 100-MHz 13C spectra of 20a . This material is
available free of charge via the Internet at http://pubs.acs.org.
J O982396R