TetrahedronLetters No. 371 PP- 3475 - 3478, 1971. PergamonFreas. hinted in Great Britain.
AN ALKYNE PROTECTING GROUP
K. M. Nicholas and R. Pettit
Department of Chemistry, Texas 78712, U. S. A.
University of Texas, Austin,
(Receivedin USA 7 June 1971; received in UK for publication14 August 1971)
Due to the greater reactivity of triple bonds to several of the more common addition reactions,
1
(i.e. reduction, hydroboration,2 and acid-catalyzed hydration3) it is generally very difficult to
selectively induce double bonds to undergo addition in the presence of triple bonds. We report
that reaction of an organic molecule containing both a double and triple bond with cobalt carbonyl
readily leads to the formation of the corresponding acetylene-dicobalt hexacarbonyl complex; the
coordinated triple bond is now inert to addition reactions thus permitting selective transforma-
4
tions of the non-coordinated olefinic bond. The facile formation and removal of the metal moiety
in high yield make these complexes useful protecting groups for triple bonds.
The complexes are readily prepared by stirring dicobalt octacarbonyl and the alkyne overnight
at room temperature in a hydrocarbon solvent.
5 The complexes may be isolated in TO-go% yield,
6
sufficiently pure for further reaction, by column chromatography over alumina. Some examples
relevant to this work are shown below.
OH OH
-
= -F (88%)
(73%)
III IV
Attempts to catalytically hydrogenate free double bonds in several different complexes were
unsuccessful. Thus, treatment of fl, -IV or -V with H in the presence of 5% Pd on carbon or Pt02
2
in EtOH or HOAc gave only starting material. Addition of cyclohexene caused no hydrogen uptake
indiiatir:g that the complexes were catalyst poisons.
3475
3476 No. 37
Reduction can be achieved, however, by treatment with diimide or BH3/HOAc. For example, the
ene-yne complex 1, upon addition of KO2C-N=N-CO2K and acetic acid in methanol, gave the reduced
a 5,6 -dehydroisoandro-
complex fi, in 92% yield. Reaction of the cobalt complex of 17-ethynl-A
sterone (IV)
- with BH3 followed by HOAc gave a 60% yield of 17-ethynlisoandrosterone-Co2(C0)6y
(VII).
-
=L=J- I\bHo I~_/-
-
A--_ / =-__
tco),coCo(C0)3 (c o),co.*.*cdco)~
v
IV
iI%+
& = VI
OH
(CO&
r”
co-..~oko)~
HO VII
Hydroboration of ene-yne complexes -II and 1 gave exclusively the products of reaction at the
double bond. Thus, treatment of _li_ with BH followed by oxidation with H202/OH- gave the diol
3
VIII
-- (45%). Complex 1 was converted to alcohols jJ and X in 62% yield in a ratio of 5:1,
10
respectively, by reaction with BH3 followed by cleavage with oxygen. Cleavage by oxygen is the
preferred method since the peroxide-base combination causes partial decomposition of the cobalt
complex.
II
V
I)BHq ) on=/- /‘== +
< F__
J--
2) 02
(co);jco....co(c 0)s ccogco-*-c oko)3
IX X
lo. 37 3477
Vinyl acetylenes, when treated with strong acids, generally iorm the product of hydration of
the triple bond.” The ene-yne-ol i reacted with a fltioboric-acetic acid mixture at 25” after 24
hours to form an intractable mixture of products. Its complex n, on the other- hand, reacted at
O” after 15 minutes to give, upon aqueous workup, a 91% yield of the diol -Xl. This facile reaction
can be attributed to the intermediacy of the metal-stabilized carbonium ion -Ila.
OH
I) HBF,+/HOAc+ HO
II f
21H20
co--co(co)3
%I (c 013
\ +f XI
OH
J--
+ 7.
)_
(co)3co-*~co(cO)3
II a
Importantly, the ligand may be recovered by oxidative degradation of the complex with
Fe(N03)3.9 H20 in 95% ethanol. Dilution with water and extraction with ether affords the product
in excellent yield. Thus the complex Similarly, the
-XI gives an 81% yield of the diol -XII.
complex -IX afforded the 1igand fi .(yO%) .
OH
XI _
Fe+3 ) HO _
f
XII
IX Fe+3 Ho-EJ- )
XIII
Further synthetic applications are being explored.
3478 No. 3-l
Acknowledgment: We thank the National Science Foundation, the Robert A. Welch Foundation and the
u. S. Army Research Office (Durham) for financial assistance.
REFERENCES
R. L. Augustine, “Catalytic Hydrogenation”, p. 70 (Marcel Decker) 1965.
2. H. C. Brown, “Hydroboration” (W. A. Benjamin, Inc.) 1962.
3. R. C. Fahey, “Topics in Stereochemistry”, vol. 3, pp. 237-342 (Interscience) 1968.
4. Seyferth (J. Amer. Chem. Sot., 92, 5520, 1970)has reported the Friedel-Crafts reactions of
diphenylacetylene-Co2(C0)6. The organic ligand was retrieved by oxidation with
(NH,,)2Ce ‘v(No3)6 in acetone.
5. H. Greenfield, H. W. Sternberg, R. A. Friedel, J. H. Wotjz, R. Markby and I. Wender,
J. Amer. Chem. Sot., 78, 120 (1956).
H
6. The complexes were difficult to obtain analytically pure. NHR analysis of the complexes
Followed by defradation and nmr and mass spectra of the resulting ligands completed the
characterization. All alcohols were converted to their trimethylsilyl ethers for mass
spectral analysis.
7. Prepared according to H. E. Stavely, J. Amer. Chem. Sot._, 2, 79 (1939).
8. No attempts were made to improve yields.
9. Complex characterized by degradation to the free ligand, m.p.=253-255”; lit.=255-257’=‘,
von L. Ruzicka and K. Hofmann, Helv. Chim. Acta, g, 1280 (1937).
IO. H. C. Brown, M. M. Midland, and G. W. Kabalka, L Amer. Chem. Sot., 2, 1024 (1971).
II. A. W. Johnson, “The Chemistry of the Acetylenic Compounds”, vol. 1, p. 56 (Edward Arnold G Co.)
1946.
