S1

Electronic Supplementary Information

CeCl3-mediated alkynylic 1,2-addition reaction of C-O acetylenic bis-lithium salts to

aldehydes and ketones. An efficient route to bis-substituted alkyne diols

Jefferson L. Princivala* and Jeiely G. Ferreiraa

Laboratório de Catálise Orgânica - Departamento de Química Fundamental-UFPE

Av. Jornalista Aníbal Fernandes s/n - Cidade Universitária - Recife-PE

CEP 50740-560 / Tel.:+55 (81) 2126-7463

Contents Page

Experimental S2

Data Analysis S3-S5

1H and 13C NMR spectra S6-S32

S2

Experimental

All solvents used in the reactions were purified by distillation prior to use. In the case of dry

THF (used to generate bis-lithium salts in the organometallic step), the solvent was dried at

reflux in the presence of pieces of metallic sodium using 1,10-phenantroline as an indicator.

The reactions were conducted in round bottom flasks fitted with rubber septa under a

positive nitrogen atmosphere flow and purified on flash silica 220-440 mesh particle size.

The reactions were monitored using aluminum TLC plates 20x20 cm on silica gel 60 of

Macherey-Nagel® and using a SHIMADZU

® 2010 Plus Gas chromatograph coupled with an

auto sampler for the flame ionization detector (FID) using N2 as the carrier gas.

The 1H at 300 MHz and

13C at 75 MHz NMR analysis were performed on a VARIAN

® Unity

Plus-300 (300 MHz) spectrometer, using deuterated chloroform (CDCl3) as solvent and Me4Si

as internal standard. The chemical shifts are expressed in ppm and coupling constants (J) are in

Hz.

General procedure for the preparation of diols 4-21

To a round bottom flask containing the propargylic alcohol (3 mmol) in THF (5 mL) at -40 0C under a dry N2 atmosphere with stirring, n-butyl lithium (6.6 mmol; 7.2 mL, 0.92 mol/L

solution in hexane) was added dropwise. After stirring the solution at the same temperature for

20 min, it was transferred to another round bottomed flask containing a previously prepared

mixture of the carbonyl compound (3mmol) and anhydrous CeCl3 (1.5 mmol) in THF (10 mL).

The reaction was monitored by TLC until consumption of the carbonyl compound, quenched

with a saturated solution of NH4Cl (2 mL) and the phases separated. The aqueous phase was

extracted with ethyl acetate (2 x 5 mL) washed with brine, dried with magnesium sulphate,

filtered, and the solvents removed using a rotary evaporator under vacuum. The crude was

purified by silica gel chromatography using n-hexane/ethyl acetate (1:1) as eluent.

S3

Pent-2-yne-1,4-diol (4) Colourless oil, yield (0.28g) 94%. 1HNMR (300 MHz;

CDCl3, ppm): δ 1.44 (3H, d, J = 6.3 Hz), 3.60 (2H, s), 4.28 (2H, d, J = 1.8 Hz), 4.57

(1H, qt, J = 6.3 Hz, J = 1.8 Hz); 13

CNMR(75 MHz; CDCl3, ppm): δ 24.0, 50.6, 58.1,

82.1, 87.5; CAS 927-57-1.

Hex-2-yne-1,4-diol (5) Colourless oil, yield (0.31g) 91%. 1HNMR (300 MHz;

CDCl3, ppm): δ 0.99 (3H, t, J = 7.5 Hz), 1.65-1.80 (2H, m), 3.99 (2H, s), 4.30

(2H, d, J = 1.5 Hz), 4.35 (1H, tt, J = 6.6 Hz, J = 1.5 Hz); 13

CNMR (75 MHz;

CDCl3, ppm): δ 9.4, 30.5, 50.4, 63.3, 82.9, 86.3; CAS 14092-35-4

Hept-3-yne-1,4-diol (6) Colourless oil, yield (0.38g) 100%. 1HNMR (300

MHz; CDCl3, ppm): δ 0.9 (3H, t, J = 7.5 Hz), 1.47 (2H, sext, J = 7.5 Hz), 1.60-

1.77 (2H, m), 3.58 (2H, s), 4.30 (2H, d, J = 1.8 Hz), 4.43 (1H, tt, J = 6.6 Hz, J

= 1.8 Hz); 13

CNMR (75 MHz; CDCl3, ppm): δ 13.6, 18.4, 39.5, 50.6, 61.9,

82.8, 86.6; CAS 18864-39-6

Non-2-yne-1,4-diol (7) Colourless oil, yield (0.47g) 100%. 1HNMR

(300 MHz; CDCl3, ppm): δ 0.90 (3H, t, J = 6.9 Hz), 1.25-1.50 (6H, m),

1.60-1.80 (2H, m), 3.31 (2H, s), 4.31 (2H, t, J = 1.8 Hz), 4.49 (1H, tt, J =

6.6 Hz, J = 1.8 Hz ); 13

CNMR (75 MHz; CDCl3, ppm): δ 13.9, 22.5,

24.8, 31.4, 37.4, 50.6, 62.2, 82.8, 86.7; CAS 98262-70-5

5-methylhex-2-yne-1,4-diol (8) Colourless oil, yield (0.38g) 100%. 1HNMR (300

MHz; CDCl3, ppm): δ 1.0 (6H, dd, J = 6 Hz), 1.88 (1H, oct, J = 6 Hz), 3.13 (2H,

s), 4.21 (1H, dt, J = 6 Hz, J = 1.5 Hz ), 4.32 (2H, d, J = 1.5 Hz); 13

CNMR (75

MHz; CDCl3, ppm): δ 17.5, 18.0, 34.3, 50.7, 67.7, 83.7, 85.3; CAS 35336-44-8

4-methylhex-2-yne-1,4-diol (9): Colourless oil, yield (0.35g) 90%. 1HNMR (300

MHz; CDCl3, ppm): δ 1.03 (3H, t, J = 7.5 Hz), 1.47 (3H, s), 1.71 (2H, q, J = 7.5

Hz), 2.88 (2H, s), 4.30 (2H, s); 13

CNMR (75 MHz; CDCl3, ppm): δ 8.93, 28.9,

36.2, 50.7, 68.6, 81.4, 89.1; CAS 920-09-2

S4

1-phenylbut-2-yne-1,4-diol (10) Solid, yield (0.49g) 100%.1HNMR (300

MHz; CDCl3, ppm): δ 2.22 (2H, s), 4.35 (2H, d, J = 1.8 Hz), 5.52 (1H, t, J =

1.8 Hz), 7.35-7.45 (3H, m), 7.5-7.6 (2H, m); 13

CNMR (75 MHz; CDCl3, ppm):

δ 51.0, 64.4, 84.8, 85.4, 126.5, 128.4, 128.6, 140.2; CAS 29021-82-7

1-(furan-2-yl)but-2-yne-1,4-diol (11) Colourless oil, yield (0.45g) 100%.

1HNMR (300 MHz; CDCl3, ppm): δ 4.35 (2H, d, J = 1.5 Hz), 5.51 (1H, t, J =

1.5 Hz), 6.35 (1H, dd, J = 3.3 Hz, J = 1.8 Hz ), 6.44 (1H, dt, J = 3.3 Hz, J = 0.9

Hz), 7.41 (1H, dd, J = 1.8 Hz, J = 0.9 Hz ); 13

CNMR (75 MHz; CDCl3, ppm): δ

50.4, 57.6, 82.7, 83.9, 107.7, 110.3, 142.9, 152.4; CAS 90111-26-5

1-(3-hydroxybut-1-yn-1-yl)cyclohexanol (12) Colourless oil, yield (0.45g)

90%. 1HNMR (300 MHz; CDCl3, ppm): δ 1.42 (3H, d, J = 6.6 Hz), 1.45-1.95

(10H, m), 3.67 (1H, s), 4.54 (1H, q, J = 6.6 Hz); 13

CNMR (75 MHz; CDCl3,

ppm): δ 23.2, 24.2, 25.1, 39.6, 57.9, 68.4, 86.1, 87.4; CAS 5111-47-7

1,1-diphenylpent-2-yne-1,4-diol (13) Colourless oil, yield (0.75g) 100%.

1HNMR (300 MHz; CDCl3, ppm): δ 1.51 (3H, d, J = 6.6 Hz), 4.64 (1H, q, J =

6.6 Hz), 7.2-7.4 (6H, m), 7.55-7.65 (4H, m); 13

CNMR (75 MHz; CDCl3, ppm):

δ 24.0, 58.3, 74.1, 86.6, 89.9, 125.9, 127.6, 128.2, 144.7; CAS 783339-46-8

(R,S)-2-metilhex-3-ino-2,5-diol. (14): Colourless oil, yield (0.35g) 91%.

1HNMR (300 MHz; CDCl3, ppm): δ 1.44 (3H, d, J = 6.6 Hz), 1.52 (6H, s), 3.13

(2H, s), 4.55 (1H, q, J = 6.6 Hz); 13

CNMR (75 MHz; CDCl3, ppm): δ 24.2, 31.2,

58.0, 64.9, 83.9, 88.6; CAS 5111-43-3

2-methyhept-3-yne-2,5-diol (15) Colourless oil, yield (0.39g) 93%. 1HNMR

(300 MHz; CDCl3, ppm): δ 0.96 (3H, t, J = 7.5 Hz), 1.49 (6H, s), 1.6-1.75 (2H,

m), 2.84 (2H, s), 4.30 (1H, t, J = 6.6 Hz); 13

CNMR (75 MHz; CDCl3, ppm): δ

9.4, 30.7, 31.3, 63.4, 65.0, 82.8, 89.5; CAS 41368-08-5

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2,6-dimethylhept-3-yne-2,5-diol (16) Colourless oil, yield (0.47g) 100%.

1HNMR (300 MHz; CDCl3, ppm): δ 0.98 (6H, dd, J = 6.6 Hz), 1.51 (6H, s),

1.85 (1H, oct, J = 6.6 Hz), 3.18 (2H, s), 4.16 (1H, d, J = 6.6 Hz; 13

CNMR (75

MHz; CDCl3, ppm): δ 17.4, 18.1, 31.2, 31.3, 34.3, 65.0, 67.5, 81.7, 90.2; CAS

5486-58-8

Hex-3-yne-1,5-diol (17) Colourless oil, yield (0.3g) 90%. 1HNMR (300 MHz;

CDCl3, ppm): δ 1.40 (3H, d, J = 6.6 Hz), 2.44 (2H, td, J = 6.6 Hz, J = 2.1 Hz),

2.73 (2H, s), 3.69 (2H, t, J = 6.3 Hz ), 4.49 (1H, qt, J = 6.3 Hz, J = 2.1 Hz);

13CNMR (75 MHz; CDCl3, ppm): δ 22.9, 24.4, 58.2, 60.8, 81.1, 84.1; CAS

488099-02-1

Hept-3-ine-1,5-diol (18) Colourless oil, yield (0.35g) 92%. 1HNMR (300

MHz; CDCl3, ppm): δ 1.0 (3H, d, J = 7.5 Hz), 1.6-1.8 (2H, m), 2.48 (2H, td, J

= 6 Hz, J = 2.1 Hz), 3.18 (2H, s), 3.72 (2H, t, J = 6 Hz), 4.31 (1H, tt, J = 6.6

Hz, J = 2.1 Hz); 13

CNMR (75 MHz; CDCl3, ppm): δ 9.4, 22.9, 30.9, 60.8,

63.6, 82.1, 82.9; CAS 1782972-32-0

6-methylhept-3-yne-1,5-diol (19) Colourless oil, yield (0.41g) 97%. 1HNMR

(300 MHz; CDCl3, ppm): δ 0.97 (6H, dd, J = 6.6 Hz), 1.83 (1H, oct, J = 6.6

Hz), 2.47 (2H, td, J = 6 Hz, J = 2.1 Hz), 2.87 (2H, s), 3.71 (2H, t, J = 6 Hz),

4.14 (1H, d, J = 6 Hz); 13

CNMR (75 MHz; CDCl3, ppm): δ 17.4, 18.1, 22.9,

34.5, 60.9, 67.9, 81.7, 82.7; CAS 20634-84-8

Hex-2-yne-1,5-diol (20) Colourless oil, yield (0.31g) 91%. 1HNMR (300 MHz;

CDCl3, ppm): δ 1.25 (3H, d, J = 6.3 Hz), 2.31 (1H, ddt, J = 16.3 Hz, J

= 6.6 Hz, J

= 2.1 Hz), 2.44 (1H, ddt, J = 16.3 Hz, J

= 6.6 Hz, J

= 2.1 Hz), 2.94 (2H, s), 3.97

(1H, sext, J = 6.6 Hz), 4.26 (2H, t, J

= 2.1 Hz);

13CNMR (75 MHz; CDCl3, ppm):

δ 22.2, 29.1, 51.0, 66.3, 80.7, 82.6; CAS 343268-16-6

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1HNMR (300 MHz, CDCl3) of 4.

S7

13CNMR (75 MHz, CDCl3) of 4.

1HNMR (300 MHz, CDCl3) of 5

S8

13CNMR (75 MHz, CDCl3) of 5

S9

1HNMR (300 MHz, CDCl3) of 6

S10

13CNMR (75 MHz, CDCl3) of 6

1HNMR (300 MHz, CDCl3) of 7

S11

13CNMR (75 MHz, CDCl3) of 7

S12

1HNMR (300 MHz, CDCl3) of 8

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13CNMR (75 MHz, CDCl3) of 8

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1HNMR (300 MHz, CDCl3) of 9

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13CNMR (75 MHz, CDCl3) of 9

1HNMR (300 MHz, CDCl3) of 10

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13CNMR (75 MHz, CDCl3) of 10

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1HNMR (300 MHz, CDCl3) of 11

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13CNMR (75 MHz, CDCl3) of 11

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1HNMR (300 MHz, CDCl3) of 12

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13CNMR (75 MHz, CDCl3) of 12

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1HNMR (300 MHz, CDCl3) of 13

S22

13CNMR (75 MHz, CDCl3) of 13

1HNMR (300 MHz, CDCl3) of 14

S23

13CNMR (75 MHz, CDCl3) of 14

S24

1HNMR (300 MHz, CDCl3) of 15

S25

13CNMR (75 MHz, CDCl3) of 15

1HNMR (300 MHz, CDCl3) of 16

S26

13CNMR (75 MHz, CDCl3) of 16

S27

1HNMR (300 MHz, CDCl3) of 17

13CNMR (75 MHz, CDCl3) of 17

S28

1HNMR (300 MHz, CDCl3) of 18

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13CNMR (75 MHz, CDCl3) of 18

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1HNMR (300 MHz, CDCl3) of 19

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13CNMR (75 MHz, CDCl3) of 19

1HNMR (300 MHz, CDCl3) of 20

S32

13CNMR (75 MHz, CDCl3) of 20