7
film NaCl): 3630,3610,3000,1460,1075,728,715; HRMS (ESI) calc’d for
C16H15BrO2Se: [M+Na]+ : 420.9318, Found 420.9316.
124.9, 120.3, 112.3, 80.6, 46.9, 30.3, 17.6; IR(neat film NaCl):
ACCEPTED MANUSCRIPT
3630,3610,3000,2940,2921,1460,1075,735,700;HRMS (ESI) calc’d for
C18H19BrO2Se: [M+Na]+ : 448.9631, Found 448.9633.
(E)-2-(3-bromo-1-hydroxy-4-(phenylselanyl)but-3-en-1-yl)-4-
methylphenol (6b):The compound 6b was prepared from 5b according
to procedure B. 2-(1-hydroxybut-3-yn-1-yl)-4-methylphenol, 5b (150mg,
0.85mmol) was dissolved in dry THF(2 ml) and K2CO3 (117 mg, 0.85
mmol) and PhSeBr (200 mg, 0.85mmol) were added to the reaction
mixture at room temperature afforded 6b, (E)-2-(3-bromo-1-hydroxy-4-
(phenylselanyl)but-3-en-1-yl)-4-methylphenol (308mg, 0.748mmol,
88%) as a yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.79 (s, 1H), 7.57
- 7.55 (m, 2H), 7.37 - 7.35 (m, 3H), 6.99 - 6.97 (d, J= 8 Hz, 1H), 6.78 (d,
J= 8 Hz, 1H), 6.7 (d, J= 1.6 Hz, 1H), 6.638 (s, 1H), 5.19 - 5.15 (m, 1H),
3.24 - 3.20 (m, 1H), 2.74 - 2.69 (dd, J= 14.4 Hz, 4Hz, 1H), 2.25 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 153.1, 133.8, 131.9, 129.7, 129.6, 129,
128.4, 128.2, 127.5, 125.8, 117, 109.4, 74.1, 42.3, 20.5; IR(neat film
NaCl): 3630,3610,3000,2923,1456,732,717;HRMS (ESI) calc’d for
C17H17BrO2Se [M]+ : 411.9577, Found 411.9574.
(1S,5S,E)/(1R,5R,E)-3-bromo-1-(2-hydroxyphenyl)-4-
(phenylselanyl)hex-3-ene-1,5-diol (8a):Prepared according to general
procedure B. To a solution of 7a, (1S,5S)-1-(2-hydroxyphenyl)hex-3-
yne-1,5-diol (250mg, 1.21 mmol) in dry THF (3 ml), K2CO3(167 mg,
1.21 mmol) and PhSeBr (285mg, 1.21mmol) was added at room
temperature to obtain 8a, (470mg, 1.06mmol, 88%) as a yellowish white
solid. 1H NMR (400 MHz, CDCl3) δ 7.37 - 7.35 (m, 2H), 7.26 - 7.16 (m,
4H), 6.96 - 6.94 (dd, J= 7.6 Hz, 1.6 Hz, 1H), 6.86 - 6.80 (m, 2H), 5.26 -
5.23 (q, J= 8.8 Hz, 1H), 5.06 - 5.02 (m, 1H), 3.79 - 3.73 (q, J= 14.4 Hz,
1H), 3.22 - 3.17 (m, 1H) , 1.27 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
155.5, 137.4, 131.1, 130.06, 130, 129.9, 129.5, 129.4, 129.2, 128.7,
127.8, 127.6, 127.1, 126.8, 126.3, 125.7, 119.7, 117.2,
113.9,74,71.8,31.8,22.1;IR(neatfilmNaCl):3630,3610,3000,2920,2150,14
57,1075,732,710; HRMS (ESI) calc’d for C18H19BrO3Se: [M+Na]+
464.9580, Found 464.9578; M.P. 74-76°C.
:
(E)-4-bromo-2-(3-bromo-1-hydroxy-4-(phenylselanyl)but-3-en-1-
yl)phenol (6c): The Compound 6c was prepared by the reaction of 5c,
(4-bromo-2-(1-hydroxybut-3-yn-1-yl)phenol (150mg, 0.622 mmol) in
dry THF (1.5ml) and K2CO3 (86mg, 0.622 mmol) and PhSeBr (147 mg,
0.622mmol) at room temperature to give 6c, (E)-4-bromo-2-(3-bromo-1-
hydroxy-4-(phenylselanyl)but-3-en-1-yl)phenol (255 mg, 0.534 mmol,
(1S,5S,E)/(1R,5R,E)-3-bromo-5-(2-hydroxyphenyl)-1-phenyl-2-
(phenylselanyl)pent-2-ene-1,5-diol (8b): Prepared according to general
procedure B. (1S,5S)-5-(2-hydroxyphenyl)-1-phenylpent-2-yne-1,5-diol,
7b (200mg, 0.74 mmol) in dry THF, , K2CO3(103mg, 0.74mmol) and
PhSeBr(176mg, 0.74mmol) to afford 8b (300mg, 0.59mmol, 80%) as a
yellowish white solid.1H NMR (400 MHz, CDCl3) δ 7.82 (s, 1H), 7.37 -
7.08 (m, 11H), 6.97 - 6.76 (m, 3H), 6.24 (s, 1H), 5.32 - 5.29 (m, 1H),
3.78 - 3.67 (m, 1H), 3.41 (s, 1H), 3.24 - 3.19 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 155.4, 140.6, 131.06, 130.1, 129.8, 129.3, 129.2, 128.5,
128.3, 127.7, 127.1, 126.9, 125.9, 119.8, 117.1, 76.1, 73.8, 48.4; IR(neat
film NaCl): 3630,3610,3000,2923,2150,1459,1076,738,705; HRMS
(ESI) calc’d for C23H21BrO3Se [M]+ : 503.9839, Found 503.9808; M.P.
148-150°C.
1
86 %) as a yellow liquid. H NMR (400 MHz, CDCl3) δ 8.43 - 8.30 (m,
1H), 7.54 - 7.52 (m, 2H), 7.35 (s, 3H), 7.29 - 7.23 (d, J= 8.8 Hz, 1H),
7.02 (d, J= 6 Hz, 1H), 6.72 ( d, J= 8.8 Hz, 1 H), 6.58 (s, 1H), 5.14 - 5.12
(m,1H), 3.74 (s, 1H), 3.18 - 3.12 (q, J= 13.6 Hz, 1H), 2.69-2.74 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 155.9, 135.3, 133.2, 133, 131.27, 131.2,
129.9, 129.6, 120.2, 113.2, 111, 69.4, 43.4; IR(neat film NaCl):
3630,3610,3000,1460,1075,728,707;
HRMS
(ESI)
calc’d
for
C16H14Br2O2Se: [M+Na]+ : 498.8423, Found 498.8425.
(E)-2-(3-bromo-1-hydroxy-4-(phenylselanyl)but-3-en-1-yl)-4-
(Z)-4-bromo-2-(4-bromo-2-hydroxy-5-(phenylselanyl)pent-4-en-2-
yl)phenol(6h):To a solution of 5h, 4-bromo-2-(2-hydroxypent-4-yn-2-
yl)phenol (100mg, 0.392mmol) in dry THF, K2CO3(54mg, 0.392mmol)
and PhSeBr(92.5mg, 0.392mmol) to obtain 6h (E)-4-bromo-2-(4-bromo-
2-hydroxy-5-(phenylselanyl)pent-4-en-2-yl)phenol (144mg, .294mmol,
75%) as a liquid. 1H NMR (400 MHz, CDCl3) δ 9.15 (s, 1H), 7.50 - 7.47
(m, 2H), 7.38 - 7.35 (m, 3H), 7.27 - 7.24 (dd, J= 8.8 Hz, 2.4 Hz, 1H),
7.17 (d, J= 2.4 Hz, 1H), 6.75 - 6.72 (m, 2H), 4.03 (s, 1H), 3.13 - 3.01 (q,
J= 32.4 Hz, 2H), 1.72 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 154.9,
133.6, 131.8, 130.9, 129.9, 129.7, 128.6, 127.6, 119.6, 111.3,
78.8,45.2,28.4;IR(neatfilmNaCl):3630,3610,3000,2920,1460,1075,735,7
00;HRMS (ESI) calc’d for C17H16Br2O2Se: [M+Na]+ : 512.8580, Found
512.8583.
chlorophenol (6d): Prepared according to general procedure B as a
1
yellow liquid; 227 mg (86%). H NMR (400 MHz, CDCl3) δ 7.91 (s,
1H), 7.56 - 7.54 (q, J= 2 Hz, 2H), 7.39 - 7.36 (m, 3H), 7.14 - 7.12 ( m,
1H), 6.87 (d, J= 2.4 Hz, 1H), 6.80 (d, J= 8.4 Hz, 1H), 6.65 (s, 1H), 5.169
(m, 1H), 3.21 - 3.15 (q, J= 14.4 Hz, 9.6 Hz, 1H), 2.76 - 2.71 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 154.2, 133.8, 131.2, 129.7, 128.9, 128.6,
127.8, 127.1, 126.7, 124.4, 118.7, 109.6, 73.7, 42.1; IR(neat film NaCl):
3630,3610,3000,1460,1075,1090,725,708; HRMS (ESI) calc’d for
C16H14BrClO2Se: [M+Na]+ : 454.8929, Found 454.8932.
(E)-2-bromo-6-(3-bromo-1-hydroxy-4-(phenylselanyl)but-3-en-1-yl)-
4-methylphenol (6e):Prepared according to general procedure B as a
colourless liquid; 237 mg (88%).1H NMR (400 MHz, CDCl3) δ 7.55 -
7.52 (m, 2H), 7.36 - 7.33 (m, 3H), 7.23 (d, J= 1.6 Hz, 1H), 6.81 (d, J= 2
Hz, 1H), 6.62 (s, 1H), 5.20 - 5.17 (q, J= 9.2 Hz, 1H), 3.18 - 3.12 (q, J=
General methods (C) for the synthesis of substituted (1S,5S/1R,5R)-
1-(2-hydroxyphenyl)hex-3-yne-1,5-diols :
14.4 Hz, 1H), 2.76 - 2.72 (dd, J= 14.4 Hz, 4.4 Hz, 1H), 2.24 (s, 3H); 13
C
NMR (100 MHz, CDCl3) δ 148.4, 133.6, 131.9, 131.7, 130.6, 129.5,
128.3, 128.1, 127.9, 127.1, 110.1, 109.4, 72.4, 41.9, 20.1; IR(neat film
NaCl): 3630,3610,3000,2923,1460,1075,738,704; HRMS (ESI) calc’d
for C17H16Br2O2Se [M]+ : 489.8682, Found 489.8713.
To a solution of 6 in dry THF, n-BuLi (3eqv.) was added in -78°C
dropwise. The temperature of the reaction medium was increased slowly
from -78°C to -55°C. After 1hr the solution of corresponding aldehydes
(1eqv.) in THF was added dropwise with vigorous stirring. After 3hrs of
stirred the resulting reaction mixture was quenched with saturated
solution of NH4Cl and extracted by EtOAc (3 x 5 ml). The organic layer
was washed with brine, dried over anhydrous sodium sulphate&
concentrated. The mixture was purified by silica column using [70:30]
Hexane:EtOAc to give 7.
(E)-2-(4-bromo-2-hydroxy-5-(phenylselanyl)pent-4-en-2-yl)phenol
(6f):Prepared according to general procedure B as a greenish liquid;
1
yield 294 mg (71%). H NMR (400 MHz, CDCl3) δ 9.19 (s, 1H), 7.52 -
7.50 (m, 2H), 7.38 - 7.30 (m, 3H), 7.21 - 7.17 (m, 1H), 7.11 - 7.09 (m,
1H), 6.88 - 6.84 (m, 2H), 6.68 (s, 1H), 4.07 (s, 1H), 3.18 (d, J= 14.4 Hz,
1H), 3.06 (d, J= 14.8 Hz, 1H), 1.76 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 155.8, 133.8, 130.6, 129.8, 129.24, 129.23, 128.7, 128, 126, 119.6,
(1S,5S/
1R,5R)-1-(2-hydroxyphenyl)hex-3-yne-1,5-diol
(7a):The
synthesis of compound 7a is synthesize using the method C, and is a
1
117.8,
110.8,
79.1,
45.5,
28.3;
IR(neat
film
NaCl):
yellowish white solid (85%). H NMR (400 MHz, CDCl3) δ 7.16 - 7.12
3630,3610,3000,2920,1460,1075,723,695;HRMS (ESI) calc’d for
(m, 1H), 7.05 (d, J= 8 Hz, 1H), 6.85 - 6.82 (m, 2H), 5.56 (s, 1H), 5.01 -
4.98 (q, J= 8 Hz, 1H), 4.49 - 4.45 (m, 1H), 2.77 - 2.62 (m, 2H), 1.40 -
1.38 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 154.6, 128.9, 127, 126.4,
119.9, 116.7, 84.2, 80.9, 72.4, 58.2, 27.9, 24.1; IR(neat film NaCl):
3620,3600,2923,2147,1460; HRMS (ESI) calc’d for C12H14O3:[M+Na]+:
229.0841, Found 229.0843; M.P. 81-83°C.
C17H17BrO2Se: [M+Na]+ : 434.9475, Found 434.9477.
(E)-2-(4-bromo-2-hydroxy-5-(phenylselanyl)pent-4-en-2-yl)-6-
methylphenol (6g):Prepared according to general procedure B as a
liquid; yield 161 mg (72%).1H NMR (400 MHz, CDCl3) δ 9.30 (s, 1H),
7.49 - 7.31 (m, 5H), 7.05 - 7.03 (m, 1H), 6.94 - 6.91 (dd, J= 8 Hz, 1.2
Hz, 1H), 6.75 - 6.71 (t, J= 7.6 Hz, 1H), 6.65 (s, 1H), 3.92 (s, 1H), 3.18 -
3.04 (q, J= 38.4 Hz, 14.8 Hz, 2H), 2.21 (s, 3H), 1.73 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 155.4, 135.1, 132, 131.7, 131.2, 130, 129.4, 127.9,
(1S,5S/1R,5R)-5-(2-hydroxyphenyl)-1-phenylpent-2-yne-1,5-diol (7b):
The synthesis of compound 7b is following the method C which was
1
explained in details in above, which is yellowish white solid (88%). H