此反应是获得碘代物的一种方法，常用的无机碘化物是碘化钠，最常用的溶剂是丙酮。

反应实例

A flame-dried, 1-L, one-necked, round-bottomed flaskequipped with a magnetic stirbar and a pressure-equalizing addition funnelfitted with a nitrogen inlet adapter is charged with 10.0 g (0.100 mol) of 5-hexen-1-ol,15.2 g (0.151 mol) of triethylamine,and 500 mL of dichloromethane . The flask is cooled in an ice-salt bath (0to −5°C) for 30 min and then9.3 mL (0.12 mol) of methanesulfonylchloride is added dropwise via the addition funnel. The reaction mixtureis stirred at −5 to −10°Cfor an additional 1 hr before being transferred to a cold 1-L separatory funneland washed successively with 150 mL of cold water, 150 mL of cold 10% (ca. 3.3N) aqueous hydrochloricacid, 150 mL of cold, saturated, aqueous sodiumbicarbonate solution, and 150 mL of cold brine. The organic layer isdried over MgSO4 and then divided into three portions. One portion is filteredinto a 300-mL, round-bottomed flask and concentrated by rotary evaporation at 8-10 mm in a 20-25°C water bath, and this is repeated with theremaining two portions to give the desired mesylate as a clear, pale-yellowoil.  Dry acetone(200 mL) and then 18.5 g(0.12 mol) of anhydrous sodium iodideare added to the above 300-mL flask, which is then equipped with a magneticstirbar and a Friedrichs condenser fitted with a nitrogen inlet adapter. Thepale-yellow solution is stirred in the dark under a positive pressure of nitrogenat gentle reflux for 4 hr. The resulting mixture is allowed to cool to roomtemperature and the acetoneis then removed by rotary evaporation at 8-10 mmin a 20-25°C water bath. Theresidue is partitioned between 50 mL of pentaneand 50 mL of 10% aqueous sodiumthiosulfate solution by swirling the flask until all of theprecipitate dissolves. The aqueous phase is discarded and the organic layer iswashed with 50 mL of brine, dried over MgSO4, filtered, and concentrated byrotary evaporation at 8-10 mmin a 20-25°C water bath. Theresidue is then passed through a 60-mL, medium porosity, sintered-glass funnelcontaining ca. 20 g ofalumina  using ca. 100 mL of pentaneas eluent. The pentane is removed by rotary evaporation at 8-10 mm in a 20-25°C water bath to give 17.44-17.97 g (83-86% overall from the alcohol) of 1 as aclear, colorless oil.

【Organic Syntheses, Vol. 81, p.121】

A. N-(tert-Butoxycarbonyl)-O-(p-toluenesulfonyl)-L-serinemethyl ester (2). A one-necked, 500-mL, round-bottomed flask equipped with a rubberseptumand magnetic stirbar was charged with 26.1 g (119 mmol)of N-(tert-butoxycarbonyl)-L-serine methyl ester (1) (Note1) and 200 mL of CH2Cl2 (Note2). The solution is cooled in an ice bath at 0°C while 0.700 g (6.0 mmol)of 4-dimethylaminopyridine (4-DMAP), 1.1 g (12 mmol) ofMe3NHCl (Note3), and 22.7 g(119 mmol) of freshly recrystallized p-toluenesulfonylchloride (TsCl) (Note4) are added. The septum is replaced with a droppingfunnelcharged with 17 mL (119 mmol) of triethylamine(Et3N) in 50 ml of CH2Cl2 which is addeddropwise to the reaction mixture at 0°Cover 40 min (Note5). The resulting slurry is stirred at 0°C for 2 hr and then poured into a mixture of 100 mLof ice, 100 mL of water, and 50 mL of 2M HCl solution. The aqueous layer is extracted with 100mL of CH2Cl2, and the combinedorganic layers are washed with two 60-mL portions of brine, dried over magnesiumsulfate,and concentrated by rotary evaporation to yield 59.4 g of a light yellow solid. This product maycontain ca. 15% of starting material and TsCl that can beefficiently removed by crystallization according to the following procedure.The solid is dissolved in 140 mL of hot diethylether,filtered, and the filtrate is allowed to cool to room temperature and then to 0°C. Once crystallization begins (Note6), a total of 250 mL of petroleum ether is added in fiveportions over 2 hr and then crystallization is allowed to proceed at −20°C overnight. The crystals arecollected by suction filtration on a Büchner funnel and air-dried togive 28.3-30.8 g (64-69%) of 2 as awhite solid , The product exhibits the following properties: mp74-76°C, lit.7a74-75°C; [α]D20+3.0 (methanol, c 2.0), lit.7b+4.6(methanol, c 2); Rf 0.24 (petroleum ether/EtOAc 3:1); IR (CH2Cl2) cm−1: 3384, 2979, 1753, 1714, 1511, 1367,1191, 1177; 1HNMR pdf(500 MHz, CDCl3) δ: 1.43 (s, 9 H), 2.46 (s, 3 H), 3.71(s, 3 H), 4.29 (dd, J = 10.1, 3.1 Hz, 1 H), 4.40 (dd, J = 10.1,3.1 Hz, 1 H), 4.50-4.53 (m, 1 H), 5.30 (d, J = 7.9 Hz, NH), 7.37 (app d,J = 7.9 Hz, 2 H), 7.77 (app d, J = 8.2 Hz, 2 H); 13C NMR (125 MHz, CDCl3) δ: 21.9, 28.4 (3 C), 53.1 (2 C), 69.7, 80.7, 128.2 (2 C), 130.1 (2 C),132.5, 145.4, 155.1, 169.2; MS (EI) m/z 314 (M+-CO2Me, 20%), 300 [(M+-OtBu),8%], 258 [(M+-BocNH2), 13%], 215 (11%), 155 (TolSO2, 43%), 57 (100%);HRMS (EI) m/z: [M - CO2Me]+ calcd for C14H20NO5S, 314.1057; found, 314.1059.

B. N-(tert-Butoxycarbonyl)-β-iodoalaninemethyl ester (3). A one-necked, 250-mL, round-bottomed flask equipped with a rubberseptumand magnetic stirbar is charged with 27.8 g (74.0 mmol)of N-(tert-butoxycarbonyl)-O-(p-toluenesulfonyl)-L-serinemethyl ester (2) and 160 mL of acetone (Note8). The solution is stirred at room temperature and 13.4 g(89.0 mmol) of NaI (Note9) is added in one portion. The reaction mixture is stirred in thedark for 3 days, after which an additional 3.3 g (22 mmol) ofNaI is added andstirring is continued for an additional day (Note10). The reaction mixture is then suction filtered through a sinteredglass funneland the filtrate is collected in a one-necked, 500-mL,round-bottomed flask. The solid is washed with acetone until it iscolorless. The solid is discarded and the filtrate is concentrated by rotaryevaporation under reduced pressure (Note11). The residual yellow oil is partitioned between 150mL of diethyl ether and 60 mL of 1M sodiumthiosulfate (Na2S2O3) solution. Theorganic layer is separated and washed with 40 mL of 1M Na2S2O350mL of brine,dried over magnesiumsulfate,filtered, and concentrated by rotary evaporation (Note11) to afford 23.2 g of a colorless oil that solidifies on standing at 0°C. The solid is dissolved in 30mL of hot (40°C)petroleum ether (bp 35-45°C),cooled to room temperature and then to 0°C.Once a precipitate appears (Note6), the mixture is cooled at −20°Cfor 1 hr and the white solid is collected on a Büchnerfunneland washed with cold petroleum ether to yield 19.4-20.0 g (80-82%) of N-(tert-butoxycarbonyl)-β-iodoalaninemethyl ester 3 as white to pale yellow crystals Compound 3 exhibits thefollowing spectroscopic and physical properties: mp 45-47°C, lit.6bmp= 51°C; [α]D20−3.7 (MeOH),c 3.0, lit.6b[α]D20= −4.0 (c 3 methanol); Rf 0.60 (petroleum ether/AcOEt 3:1); IR (CH2Cl2) cm−1: 1163, 1259, 1422,1714, 1748, 2986, 3054, 3424; 1H NMR pdf(500 MHz, CDCl3) δ: 1.47 (s, 9 H), 3.55-3.67 (m, 2 H),3.81 (s, 3 H), 4.53-4.54 (m, 1 H), 5.36 (d, J = 6.4 Hz, 1 H); C NMR (125 MHz,CDCl3 δ: 8.6, 29.0 (3 C), 53.7, 54.4, 81.2, 155.5, 170.8,; MS(EI) m/z 270 (M+-CO2Me 25%), 214 [(M+-Boc), 8%], 57 (100%); HRMS (ESI) m/z:[M + Na]+ calcd for C9H16INO4, 352.0016; found, 352.0021; Anal. Calcd for C9H16INO4: C, 32.8; H 4.9; N,4.3. Found: C, 33.2; H 4.8; N, 4.1.

【Organic Syntheses, Vol. 81, p.77 (2005).】