Page 858 - Advanced Organic Chemistry Part B - Reactions & Synthesis

834 Palladium-catalyzed procedures have also been developed for addition of stannanes to
alkynes, 143 and these reactions usually occur by syn addition.
CHAPTER 9
Carbon-Carbon -PPh (C H ) Sn CH 3
4 9 3
PdCl 2 3
Bond-Forming Reactions PhC CCH 3 + (C H )SnH
4 9
of Compounds of Boron, Ph
Silicon, and Tin H
Hydrostannylation of terminal alkynes can also be achieved by reaction with stannyl-
cyanocuprates.
HOCH CH 2 H
2
) SnCu(CN)Li
HOCH CH C CH + (CH 3 3 2
2
2
H Sn(CH )
3 3
CH 3
Ref. 144
(C H O) CH H
(C H O) CHC CH + (n-C H ) SnCu(CN)Li 2 2 5 2
2 5
4 9 3
2
C H H Sn(n-C H )
4 9 3
4 9
Ref. 145
These reactions proceed via a syn addition followed by protonolysis.
R H
RC CH + R′ SnCu(CN)Li 2 SOH R H
3
R″ Cu SnR′ 3 H SnR′ 3
″R

Allylic stannanes can be prepared from allylic halides and sulfonates by
displacement with or LiSnMe 3 or LiSnBu . 146 They can also be prepared by
3
Pd-catalyzed substitution of allylic acetates and phosphates using C H AlSn
2
5 2
n-C H . 147
9 3
4
Another major route for synthesis of stannanes is reaction of an organometallic
reagent with a trisubstituted halostannane, which is the normal route for the preparation
of aryl stannanes.
)
CH O MgBr + BrSn(CH ) CH O Sn(CH 3 3
3 3
3
3
Ref. 148
143
H. X. Zhang, F. Guibe, and G. Balavoine, Tetrahedron Lett., 29, 619 (1988); M. Benechie, T. Skrydstrup,
and F. Khuong-Huu, Tetrahedron Lett., 32, 7535 (1991); N. D. Smith, J. Mancuso, and M. Lautens,
Chem. Rev., 100, 3257 (2000).
144 I. Beaudet, J.-L. Parrain, and J.-P. Quintard, Tetrahedron Lett., 32, 6333 (1991).
145 A. C. Oehlschlager, M. W. Hutzinger, R. Aksela, S. Sharma, and S. M. Singh, Tetrahedron Lett., 31,
165 (1990).
146
E. Winter and R. Bruckner, Synlett, 1049 (1994); G. Naruta and K. Maruyama, Chem. Lett., 881 (1979);
G. E. Keck and S. D. Tonnies, Tetrahedron Lett., 34, 4607 (1993); S. Weigand and R. Bruckner,
Synthesis, 475 (1996).
147 B. M. Trost and J. W. Herndon, J. Am. Chem. Soc., 106, 6835 (1984); S. Matsubara, K. Wakamatsu,
J. Morizawa, N. Tsuboniwa, K. Oshima, and H. Nozaki, Bull. Chem. Soc. Jpn., 58, 1196 (1985).
148
C. Eaborn, A. R. Thompson, and D. R. M. Walton, J. Chem. Soc. C, 1364 (1967); C. Eaborn,
H. L. Hornfeld, and D. R. M. Walton, J. Chem. Soc. B, 1036 (1967).