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Procedure for tinhydride reaction of homopropargyl benzosulfonate 1: A solution of Bu3SnH (4.6 mmole) and AIBN (4.6 mmole) in 50 mL of dry benzene was added to a refluxing
solution of 2 (4.6 mmole) in 90 mL of dry benzene over a period of 10 h via a syringe pump. After
an additional 4-6 h, the reaction mixture was concentrated in vacuo. Purification
of the residue by flash column chromatography on silica gel (gradient elution; 10%
EtOAc-hexanes then 100% EtOAc) furnished in order of elution, the cyclic α-tributyltin
substituted sultone 7 and α,β-unsaturated cyclic sultone 2. 1H NMR, IR and MS spectra of 2a and 2b are identical with those provided in the literature (ref.
[8]
) Analytical data for 7a: 1H NMR (300 MHz, CDCl3) δ 0.73 (t, 3 CH3), 0.40-1.30 (3 × 3 CH2), 2.17 (br dd, 1 H), 2.41 (qd, 1 H), 4.57 (d, 1 H), 4.66 (m, 1 H), 4.80 (td, 1 H),
5.21 (dt, 1 H), 7.43 (dd, 1 H), 7. 53 (t, 1 H), 7.68 (d, 1 H), 7.79 (d, 1 H), 8.18
(d, 1 H), 8.99 (d, 1 H). 13C NMR (75 MHz, CDCl3) δ 9.9 (t, 3 CH2), 12.0 (q, 3 CH3), 25.6 (t, 3 CH2), 27.0 (t, 3 CH2), 27.3 (t), 37.1 (d), 1.4 (d), 69.6 (t), 119.9 (d), 124.6 (d), 124.9 (d), 126.2 (d),
127.0 (s), 134.9 (d), 137.6 (s), 144.6 (s), 148.3 (d). IR(neat)1334 (SO2), 1150 (SO2) cm-1
. MS m/e (rel. intensity) 552 (M+-1, 10), 405(40), 361(97), 294(70), 262 (M+-SnBu3, 100). Analytical data for 7b: 1H NMR (300 MHz, CDCl3) δ 0.74 (t, 3 CH), 0.50-1.30 (3 × 3 CH2), 2.11 (br d, 1 H), 2.51 (qd, 1 H), 2.88 (s, 2 CH3), 3.78 (dd, 1 H), 4.63 (dd, 1 H), 4. 81 (m, 2 H), 7.15 (d, 1 H), 7.35 (d, 1 H), 7.
43 (t, 1 H), 7.51 (t, 1 H), 7.77 (d, 1 H), 8.24 (d, 1 H). 13C NMR (75 MHz, CDCl3) δ 10.2 (t, 3 CH2), 12.0 (q, 3 CH3), 25.6 (t, 3 CH2), 27.0 (t, 3 CH2), 27.6 (t), 43.8 (d), 43.8 (q, 2 CH3), 52.4 (d), 70.1 (t), 112.9 (d), 115.9 (d), 121.3 (d), 122.8 (d), 123.1 (d), 125.5
(d), 128.1 (s), 130.5 (s), 135.1 (s), 150.5 (s). IR(neat)1340 (SO2), 1153 (SO2) cm-1
. MS m/e (rel. intensity) 594 (M+ + 1, 25), 538(25), 332(24), 240(100).
