J. Org. Chem. 1989,54,6075-6079 steam distilled. Pure (2)-1-bromo-1-heptene came out as colorless liquid, 6.66 g (84%). GC analysis showed the isomeric purity to be 99% Z;IFt (neat): Y 3000,1635,1470,1300,700 cm-'; 'H NMR (CDCl,/TMS) S 6.07 (m, 2 H), 2.17 (m, 2 H), 1.33 (m, 4 H), 0.87 (t, 3 H); 13C NMR (CDC13/TMS) 6 134.46, 107.48, 31.31, 29.54, 27.87, 22.42, 13.75.
6075
(E)-PhCH=CHI, 42599-246; (E)-BuCH=CHB(OH)*, 42599-188; (E)-Cl(CH2)3CH=CHB(OH)z,37490-32-7; (E)-(CH,),CCH= CHB(OH)2, 86595-37-1; Cl(CH2)sC=CH, 14267-92-6; (2)BrCH=CH(CH2)3Cl, 88357-37-3; (E)-CH3(CH2)4CH= CHBBr2.SMe2,123507-49-3; (E)-2-cyclohexyl-l-ethenylboronic acid, 37490-33-8; (E)-1-octenylboronic acid catechol ester, 73349-13-0; (E)-2-cyclohexyl-l-ethenylboronic acid catechol ester, 37490-23-6; (E)-2-phenyl-l-ethenylboronic acid catechol ester, 6783-04-6; (E)-3-hexenylboronic acid catechol ester, 94427-77-7; (Z)-l-bromo-2-cyclohexyl-l-ethene, 42843-50-5; (E)-l-bromo-2cyclohexyl-1-ethene,67478-59-5; (E)-1-hexenylboronic acid catacid echol ester, 37490-22-5; (E)-5-chloro-l-pentenylboronic catechol ester, 37490-27-0; (E)-3,3-dimethyl-l-butenylboronic acid catechol ester, 37490-25-8; (E)-2-cyclohexyl-l-iodo-l-ethene, 42599-23-5; (2)-2-cyclohexyl-l-iodo-l-ethene, 67404-69-7; cyclohexylethyne, 931-48-6.
Registry No. H C e C B u , 693-02-7; (2)-BrCH=CHBu, 13154-12-6; (E)-BrCH=CHBu, 13154-13-7;H C d P r , 627-19-0; HC=C(CH2)4CH3, 628-71-7; HC=C(CHZ)&HS, 629-05-0; PhCECH, 536-74-3; EtCECEt, 928-49-4; (2)-BrCH=CHPr, 31849-75-9; (E)-BrCH=CHPr, 31849-76-0; (2)-BrCH=CH(CH2)4CH3,39924-57-7; (E)-BrCH=CH(CH2)4CH3,53434-74-5; (2)-BrCH=CH(CH2)5CH3, 42843-49-2; (E)-BrCH=CH(CH2)5CH3, 51751-87-2; (2)-PhCH=CHBr, 588-73-8; (E)PhCH=CHBr, 588-72-7; (2)-EtCH=C(Br)Et, 16645-01-5; (E)EtCH=C(Br)Et, 42843-52-7; (E)-CH3(CH2),CH=CHB(OH)2, Supplementary Material Available: 'H NMR spectrum of 42599-16-6; (E)-PhCH=CHB(OH)z, 6783-05-7; (Z)-ICH=CHthe compound [Z]-l-iodo-5-chloro-l-pentene (1page). Ordering (CH2)5CH3, 52356-93-1; (Z)-ICH=CHBu, 16538-47-9; (2)information is given on any current masthead page. ICH=CH(CHJ,Cl, 95835-51-1; (E)-ICH=CHC(CHJ,, 61382-454;
Vinylic Organoboranes. 14. A Stereospecific Synthesis of (E)-1-Halo-1-alkenesfrom l-Alkynes1p2 Herbert C. Brown,* Tsutomu Hamaoka? Nair R a ~ i n d r a n Chitti , ~ ~ S~brahrnanyam,~~ Vishwanatha S ~ m a y a j iand , ~ ~Narayan G. Bhat3e H. C. Brown and R. B. Wetherill Laboratories of Chemistry, Purdue University, West Lufuyette, Indiana 47907 Received February 22, 1989 The reactions of (E)-1-alkenylboronicacids and their esters and (E)-1-alkenyldibromoborane-dimethylsulfide complexes with iodine under various conditions were investigated. All of these compounds react with iodine in the presence of base, producing (E)-1-iodo-1-alkenes in excellent yields and in very high stereochemical purities. A stereospecific synthesis of (E)-l-bromo- and 1-chloro-1-alkenesis herein described, based on (2)-1-alkenylboronic acids and esters. These reactions appear to be general. The above procedures provide convenient stereospecific syntheses of (E)-1-halo-1-alkenes. A plausible mechanism in each case has been discussed.
Introduction Synthetic applications of alkenylboranes have been steadily increasing over the past decade? One of the areas we focused our attention on was the synthesis of stereochemically pure (E)-and (Z)-l-hal~-l-alkenes.~'These vinyl halides are very useful intermediates in the synthesis (1) For part 13 in this series, see: Brown, H. C.; Subrahmanyam, C.; Hamaoka. T.: Ravindran. N.: Bowman, D. H.; Misumi, S.; Unni, M. K.; Somayaji,'V.; Bhat, N. G: J.'Org. Chem., preceding paper in this issue. (2) For preliminary reports, see: (a) Brown, H. C.; Hamaoka, T.; Ravindran, N. J. Am. Chem. SOC. 1973, 95, 5786. (b) Brown, H. C.; Somayaji, V. Synthesis 1984, 919. (3) (a) Visiting Scholar on funds provided by the Fuji Photo Film Company Ltd., Tokyo, Japan. (b) Postdoctoral research associate on grants provided by G. D. Searle and Co., Chicago, IL, and the National Science Foundation (Grant No. 27742x3. (c) Postdoctoral research associate on Grants CHE-79-18881 and 6449 from the National Science Foundation. (d) Postdoctoral research associate on Grant ARO DAAG 29-79-C-0027 from the United States Army Research Office. (e) Postdoctoral research associate on Grant CHE-8414171 from the National Science Foundation. (4) (a) Brown, H. C.; Campbell, J. B., Jr. Aldrichimica Acta 1981,14, 3-10. (b) Negishi, E. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E.W., Eds.;Pergamon Press: New York, 1983; Chapter 45.8, Vol. 7, pp 303-322. ( 5 ) Brown, H. C.; Bowman, D. H.; Misumi, S.; Unni, M. K. J. Am. Chem. SOC. 1967,89,4531. (6) (a) Brown, H. C.; Hamaoka, T.; Ravindran, N. J.Am. Chem. SOC. 1973.95.6456. (b) Brown, H. C.: Blue, C. D.;Nelson, D. J.; Bhat, N. G. Vinylic Organoboranes. 12. J. Org. Chem., first of four articles in this isnue. (7) (a) Kabalka, G. W.; Gooch, E. E.; Hsu, H. C. Synth. Commun. 1981, I f , 247. (b) Kalbalka, G. W.; Sastry, K. A. R.; Somayaji, V. Heterocycles 1982,18, 157. (c) Kabalka, G. W.; Sastry, K. A. R.; Knapp, F. F.; Srivastava, P. C. Synth. Commun. 1983,13, 1027.
of biologically important molecules, such as insect sex pheromones, containing 1,3-diene grouping. For example, was synbombykol ((10E,12E)-10,12-hexadecadien-l-ol) thesized by the palladium-catalyzed cross-coupling between alkenylborane and alkenyl halide (eq lhS Similarly,
Bornbykol
[10E,12E1
by using the appropriate alkenylborane and alkenyl halide, the other three (102,122 10E,122 1OZ,12E) isomers were synthesized.8 Other sex pheromones with E,Z or E$ diene configuration have also been p r e ~ a r e d . We ~ had earlier reported the synthesis of pure (Z)-l-halo-l-alkeneslJ from 1-halo-1-alkynes and (E)-1-alkenylboronic acids. In view of the growing synthetic importance of these vinyl halides, it was desirable to have available a convenient synthesis of their geometrical isomers, (E)-1-halo-1-alkenes. The (8) Miyaura, N.; Suginome, H.; Suzuki, A. Tetrahedron Lett. 1983,24, , lOZ I. CO"
(9) Cassani, G.; Massardo, P.; Piccardi, P. Tetrahedron Lett. 1982,24, 2513.
0022-3263/89/1954-6075$01.50/00 1989 American Chemical Society
6076 J. Org. Chem., Vol. 54, No. 26, 1989
Brown et al.
Table I. Synthesis of (E)-1-Iodo-1-alkenes % of
R
'c= H
/
R n-C6H13 n-C6H13 c-CEHI1
Cl(CHz)3 Cl(CH:!)3 c-CEHII t-CdHB C6H6
c
R
\ 5x2
procedure"
X2 (OH), Brz.SMe2
\
B A B A B
Brz.SMez (OH):! Br2.SMez (OW2 (OH),
c,r
A
A
c /I
H/
>99 95 >99 93 98 >99 >99 >99
A
(OH):!
'c=
/H
H/c=
yield,b % 80 (100) 66 83 (100) 57 (74) 78 (91) 51 (74) 85 (100) 79 (93)
\ti
5 7 2
OProcedures A and B are as explained in the Experimental Section. *GC yields in parentheses using n-hexadecane as an internal standard.
present paper describes such an efficient method for the preparation of these compounds in high yields and in excellent stereochemical purities. We recently reported the synthesis of alkyl bromides'O and alkyl iodides" from trialkylboranes and the corresponding halogens under basic conditions. However, similar reactions with trialkenylboranes or dialkenylborinic acids resulted in the formation of dienes instead of alkenyl halides. This problem was overcome by utilizing alkenylboronic acids and their derivatives. Iodination of ( E ) -1-Alkenylboronic Acids. Formation of (E)-l-Iodo-l-alkenes. Catecholborane hydroborated2 1-alkynes, giving the catechol esters of the corresponding (E)-1-alkenylboronicacids. Initial experiments indicated that catechol interfered with the base-induced reaction of iodine with the boronic acid. However, pure (E)-1-alkenylboronic acid could be prepared by a simple treatment with water. An ethereal solution of the boronic acid was treated with 3 equiv of sodium hydroxide, followed by 1 mol equiv of elemental iodine at 0 "C. After the reaction mixture stirred for 0.5 h and a workup, pure (E)-1.-iodo-1-alkenewas obtained in nearlv" auantitative . yield (eq 2). R C = C H + HB,
--+
Table 11. lH and 'SC NMR Spectral Data of the (E)-1-Iodo-1-alkenes
-CHZ-HC=CHI 2 1 3 (E)-1-iodo1-alkene (E)- 1-iodo1-octene (E)-5-chloro-l-iodo1-pentene (E)-2-cyclohexyl-liodo-2-ethene (E)-3,3-dimethyl-liodo-1-butene
13C
,
1H
13C
5.9 (d)
77.3 6.43 (d/t) 144.9 2.42 (m) 44.5
146.7 2.1 (m) 36.1
5.84 (d) 74.1 6.45 (4)
151.8 2.4 (m) 44.8
5.4 (d)
158.1
73.0 6.4 (d)
34.1
alkynes, giving the corresponding alkenyldibromoboranedimethyl sulfide complexes (eq 3). We have rxently R. WR') \ I ,C=C \ H' BBr, .SM% I
HBBr, .SM% RC ICH(R')
(3)
standardized the procedure for the conversion of these complexes into the corresponding alkenylboronic acids and esters15 (eq 4).
"\
'B-o
H2O
13C
74.4 6.5 (d/t)
,c=c / H I
1H
5.9 (d)
R\ H
3
2
1
1H
/ H(R')
\
Y3
The geners procedure outlined above workeL very well for both simple and branched 1-alkynes (see Table I). In all cases the stereochemical purities were >98%, as determined by gas chromatographic analysis. The 'H and 13C spectral data of these (E)-1-iodo-1-alkenes are described in Table 11. Iodination of (E)-1-Alkenyldibromoborane-Dimethyl Sulfide Complexes. Formation of (E)-1Iodo-1-alkenes. Development of the dibromoboranedimethyl sulfide (HBBr,.SMe2) reagent13 opened up yet another door to the chemistry of vinylboranes. This reagent cleanly monohydroborate~'~ terminal and internal (10) Brown, H. C.; Lane, C. F. Tetrahedron 1988,44, 2763. (11)Brown, H. C.; Rathke, M. W.; RogiE, M. M.; De Lue, N. R. Tetrahedron 1988,44, 2751. (12) Brown, H. C.; Gupta, S. K. J. Am. Chem. SOC.1972, 94, 4370. (13) Brown, H. C.; Ravindran, N. Inorg. Chem. 1977,16, 2938. (14) Brown, H. C.; Campbell, J. B., Jr. J. O g . Chem. 1980, 45, 389.
(4)
\
R
H'
\ / H
/ H(R') \ B(OR"),
However, direct conversion of alkenyldibromoboranedimethyl sulfide complexes into (E)-1-iodo-1-alkenes means a simple one-pot synthesis, avoiding the isolation of the intermediate boronic acids. Consequently, we reacted (E)-1-octenyldibromoborane-dimethylsulfide with 1 equiv of iodine under the influence of 5 equiv of base. The usual workup of the reaction mixture gave (E)-liodo-1-octene in 66% (isolated) yield. This method was equally efficient for other simple and branched alkynes as well (see Table I and Experimental Section for details). Mechanism. The formation of (E)-1-iodo-1-alkenes may be envisioned in various ways. (i) By a direct displacement of the neutralized boronic acid moiety with iodine (eq 5). This is analogous to the (15) Brown, H. C.; Bhat, N. G.; Somayaji, V. Organometallics 1983,
2, 1311.
J. Org. Chem., Vol. 54, No. 26, 1989 6077
Vinylic Organoboranes. 14
mechanism proposed for the formation of (E)-1-iodo-1alkenes in the iodination of vinylsilanes.ls However, the failure of phenylboronic acid and other alkylboronic acids to give the corresponding iodides under similar reaction conditions rules out this mechanism. (ii) An anti-addition syn-elimination sequence could give E iodides. However, in the presence of a base and a t low temperatures, this syn elimination is unlikely. Moreover, the time involved (usually 0.5 h) is insufficient for any significant addition of iodine. Further, the following experiment showed further support against this mechanism. Addition of 1.2 mmol of iodine to a vigorously stirred solution of 3.0 mmol of (E)-1-octenylboronic acid in ether and 9.0 mmol of sodium hydroxide resulted in an instantaneous disappearance of iodine (color). However, analysis of the ethereal layer showed the presence of 0.44,1.02, and 1.21 mmol of octenyl iodide in 1, 5, and 15 min, respectively. A similar reaction of 3.0 mmol of boronic acid with 1.2 mmol of iodine was performed without the base. After 10 min, the excess iodine was destroyed, and the product was treated with base. Formation of
