J. CHEM. SOC. PERKIN TRANS. I 1988 Unusual Stereoselection in the Reaction of Dianions Derived from 1-Phenylsulphonylalkan-2-01s with Electrophilic Reagents Rikuhei Tanikaga," Ken Hosoya, and Aritsune KajiDepartment of Chemistry, Faculty of Science, Kyoto University, Kitashiraka wa, Sakyo -ku, Kyoto 606,Japan ~~ The stereochemistry in the reaction of dianions of 1 -phenylsulphonylalkan-2-ols (1) with electrophilic reagents such as alkyl halides and aldehydes is discussed. The reaction takes place regioselectively at the m-position to the sulphonyl group to form a new chiral centre. In tetrahydrofuran the sterically more crowded erythro-isomer is obtained as the major product in a good diastereoisomeric ratio (50-1 00 d.e.). Additives such as HMPA and bulky diamines greatly influence the stereoselectivity of the reaction.The co-ordination of tetrahydrofuran molecules with a metal cation is considered to play an important role in the reaction. Dianions are widely used in organic synthesis, but the stereo- chemistry of their carbon-carbon bond formation has not fully been elucidated. It has been briefly reported that the dianions of p-hydroxyesters or p-hydroxy sulphoxides react with electro- philic reagents to afford the threo-isomers as major products; '*2 these findings may be explained by the intramolecular chel- ation3 between an alkoxide anion and a polar carbonyl or sulphinyl group via a lithium counter cation (see below). The dianions4--8 of 1-phenylsulphonylalkan-2-01s (p-hydroxy sulphones) have also been widely used in organic synthesis,'.lo and Kozikowski's group recently reported that treatment of the dianions of 1-phenylsulphonylpropan-2-01(la) with alkyl halides (e.g. methyl iodide or Ally1 bromide) in tetrahydrofuran (THF) generated preferentially the sterically more crowded erythro-isomers (Scheme l).'' OH OH PhSO, i,ii , phso2+ R erythro -(2a 1 + PhSOJ I R threo -(2a) Scheme 1. Reagents: i, BuLi (2 equiv.); ii, alkyl halide These results are quite different from those obtained in the reaction of dianions derived from P-hydroxy esters or p-hydroxy sulphoxides and suggest that the reaction of the dianion of (la) may proceed through a different stereochemical course. Here we report the stereochemistry in the reaction of the dianions of 1-phenylsulphonyl alkan-2-01s with electrophilic reagents such as alkyl halides, dimethyl sulphate, and aldehydes under a variety of conditions, and discuss the conformation of the dianion in the reaction.Results and Discussion When a solution of the dianion generated from l-phenyl-sulphonylundecan-2-01 (lc) and butyl-lithium (2.2 equiv.) in THF at -78 "Cl2 was quenched with D,O, a product monodeuteriated (lc) at the position a to the sulphonyl group was obtained quantitatively, but the stereoselectivity in this lithiation step could not be determined because its diastereoiso- mers were not separable by any methods. The alkylation of the dianion of (1) was carried out as in Scheme 2. A R2 erythro -(21 + P hSO, 4:R' R2 threo -(2 1 Scheme 2.Reagents: i, BuLi (2 equiv.); ii, R2X or (MeO),SO, After transforming compounds (1) into their corresponding dianions in THF at -78 "C, treatment of the dianions with alkyl halides or dimethyl sulphate afforded, as expected, the products (2) alkylated at the position ato the sulphonyl group in good yields. The configurations of these products were assigned on the basis of the coupling constant JHolHBtby 400 MHz 'H n.m.r. analysis. The results are listed in Table 1. -f Since the hydroxy and the phenylsulphonyl groups of (1) are close to each other via intramolecular hydrogen bonding, the coupling constant JHmHBin erythro-(2) must be smaller than that in threo42). See, E.Brunet, J. L. Garcia Ruano, M. C. Martinez, and J. D. Rodriguez, Tetrahedron, 1984, 40,2023. W. E. Truce and T. C. Klingler, J. Org. Chem., 1970, 35, 1834. M. Julia, et al., Tetrahedron, 1986, 42, 2475. 2398 Table 1. Alkylation reaction of the dianion of (1) Run R' (1) 1 Me (la)b 2 Me (la)b3 Me (la)b 4 Me (la)b 5 Me (la)b 6 Me (la)b 7 Bu' (lb) 8 Bu' (la) 9 C9HI9 (1c) 10 C9H19 (Ic) 11 C9H19 (Ic) 12 CH,Ph (Id) 13 CH,Ph (la) J. CHEM. SOC. PERKIN TRANS. I 1988 R2X (2) Yield ()a eryrhro: threo Me1 (2a) 98 51:49' (MeO),SO, EtI (2a) (2b) 96 57 83: 17' 61:39' C8H 171 (2c) 45 83: 17' CH ,=CHCH, Br (24 83 73:27' Me,C=CHCH,Br (2e) 72 78:22' Me1 (2f) 72 78:22' CH,=CHCH2Br (2g) 78 80:20d Me1 (2h) 72 78:22' (MeO),S02 (2h) 87 92:8' CH,=CHCH2Br (2i) 81 85: 15' Me1 (2j) 62 85: 15' CH,=CHCH,Br (2k) 69 98:2' a Isolated yield.Enantiomerically pure (2s)-(la) was used. 'The ratio was determined by h.p.1.c. analysis. 'The ratio was determined by the yield of each diastereoisomer isolated. Table 2. Effects of additives on the alkylation reaction run Run (1)" R2X Solvent Additive (equiv.) Yield () erythro :threo 1 (18) CH,=CHCH,Br THF None 83 73:27' 2 (la) CH,=CHCH,Br THF HMPT (2) 79 58:42d 3 (la) CH,=CHCH,Br Ether None 7" 52:48' 4 CH,=CHCH,Br Ether HMPT (2) 83 51 :49' 5 CH,=CHCH,Br THF TMEDA (2) 82 85: 15' 6 CH,=CHCH,Br THF DABCO (2) 67 84: 16' 7 Me1 THF None 40 76: 24' 72 78:22/ 8 Me1 Ether None 28 58:42f 9 Me1 Ether THF (I) 50 82: 181 10 11 Me1 Me1 THF THF HMPT(2) TMEDA (2) 72 35 " 56:44' 72:28' 12 Me1 THF 12-crown-4 (2) 17" 60:40' 'R' as shown in Table 1.Isolated yield. 'Determined by the yield of each diastereoisomer isolated. 'Determined by h.p.1.c. The reactions we5 carried out at -78 "C and quenched in 30 min. J After 30 min at -78 OC, the reaction mixture was warmed to room temperature over 2 h and then quenched. Interestingly in these alkylation reactions, the sterically more crowded erythro-isomers were always obtained as major iso- mers. Although the methylation of (la) with methyl iodide (run 1) yielded a 51:49 erythro :threo diastereoisomeric mixture the methylation of (lc) (run 9) and (la) (run 12) yielded 78:22 and 85 :15 diastereoisomeric mixtures, respectively, probably because of the steric effect of the alkyl side chain of (1). Similar effects were observed in the allylation reactions (run 5,8,11, and 13), and especially with (la) where a bulky benzyl side chain produced only erythro-(2k).The erythro :threo ratio increased with increasing bulkiness of the alkylating reagent e.g. methyl- ation of (la) with methyl iodide (run 1) that with dimethyl sulphate (run 2), ethylation of (la) (run 3) octylation of (la) (run 4), methylation of (lc) with methyl iodide (run 9) that with dimethyl sulphate (run lo), and methylation of (Id) (run 12) allylation of (Id) (run 13).These stereoselections are kinetically controlled because no isomerization was observed on treatment of the isolated erythro-isomer (2d) with butyl- lithium (2.2 equiv.) at room temperature. It may be concluded that the bulkiness of the alkyl side chain of (1)and the alkylating reagent influences the unusual stereoselection. Effects of Additives on the Alkylation Reactions.-The effects of additives on the allylation reaction of (la) and methylation reaction of (lc) were investigated. The results are listed in Table 2. When bulky N,N,N',N'-tetramethylethylenediamine (TMEDA) or diazabicyclo2.2.2octane (DABCO) having the ability to coordinate with lithium cation were added in THF, the eryttthro-isomers were obtained as major products in good diastereoisomeric ratios as for reactions in the absence of additives (runs 5, and 6,and ll).On the other hand, when hexamethylphosphoric triamide (HMPT) forming the 'bare' solvent separated anion l4 or lithium-selective ionophore 12- crown-4 * were employed as additives, stereoselection was found to be poor (runs 2, 9, and 12). Although the stereo- selectivity was not observed when diethyl ether (ether) instead of THF (run 3 and 8) was used, addition of 1 equiv. of THF in ether led to high stereoselectivity. These results strongly sug- gested that lithium counter cations, THF solvent, and bulky diamine additives influence the stereoselection. Recently, the co-ordination of THF molecules with lithium counter cations has been observed in the reaction of carbanions J.CHEM. SOC. PERKIN TRANS. I 1988 Table 3. Reaction of the dianions of (1) with aldehydes Run (1)a 1 (14 2 (143 (la) 4 (1b) 5 (1b)6 (lb)7 (14 R2 (3) Yield () C9H19 (34 82 (3b) 73c1 lH23 -CH,CH(Me)(CH,),CH=Me, (3) 78 C9H 19 (34 52 49c1 lH23 -CH,CH(Me)(CH,),CH=Me, (3f) 45 Pr (3g) 84 Diastereoisomer ratio 80:20' 8O:2Od e 80:20' 81 : 19' e 64:36' R' as shown in Table 1. Isolated yield. Determined by h.p.1.c. analysis. Determined by the yield of each diastereoisomer. Not determined. in THF. l6 If this co-ordination occurs during the reaction of the dianion, the bulky phenylsulphonyl group and the alkoxide anion co-ordinating some THF molecules via the lithium counter cation may be located in the anti-periplanar position because of the steric repulsion (Scheme 3).The alkylation R,' -QJ O'Li' -)PhS024.1PhS0,-R2 B ery thr o Scheme 3. reaction must, therefore, proceed via reagent attack from the stericially less hindered site B rather than site A to give an evythro-isomer (2) as a major product (see Table 4for analytical data). All findings in the alkylation reactions listed in Table 1 and 2 strongly support this conformation of the dianion of (1). It may be concluded that the chelating ability of a sulphonyl group is lower than that of the polar sulphinyl and carbonyl groups, and the co-ordinating ability of THF may play an important role. These stereoselections may be peculiar to the reaction of the dianion of (1).Reaction with Aldehydes.-Reactions were carried out in THF at -78deg;C and the 1,3-diols (3) were obtained in good yield (Scheme 4).The results are listed in Table 3, analytical data OH i.ii p so2f Rf Phso2amp;RI HO (11 (31 Scheme 4. Reagents: i, BuLi (2equiv.); ii, R2CH0 are given in Table 4.Since these 1,3-diols have produced two additional chiral centres, four kinds of diastereoisomers may be obtained, but only two of them were detected by h.p.1.c. analysis,* and were separated by silica gel column chromatography. Their n.m.r. spectra revealed that the major isomer had a 1,3-syn conformation and the minor isomer. had a 1,3-anti conforma- tion,t and that the stereochemistry at the a-position to the sulphonyl group in both isomers was the same as that of (2).A diastereo-face differentiating reaction is observed at moderate rate. Table 4. Data for compounds (2) and (3) Calculated () Found () C H C H 56.05 6.59 56.15 6.5 57.87 7.06 57.9 7.35 65.35 9.03 65.1 9.25 59.97 6.71 60.25 7.1 62.66 7.51 62.3 7.75 60.91 7.86 61.15 7.7 63.80 7.85 64.0 8.0 66.22 9.26 66.0 9.1 66.18 6.25 66.0 6.25 64.01 9.05 64.0 9.3 65.59 9.44 65.9 9.2 64.37 8.53 64.35 8.55 66.29 9.61 65.95 9.4 67.56 9.92 67.2 10.0 66.63 9.15 66.35 8.85 65.59 9.44 65.15 9.0 a All products were diastereoisomeric mixtures. These facts indicated that the reactions of the dianions of (1) with aldehydes proceed via a similar stereochemical course to the alkylation reactions, and also that the chelation of the carbonyl group of aldehydes with the lithium cation may play an important role in the stereoselection at the other chiral point.Recently, it has been reported that in a lithiated E-sulphonyl carbanion the lithium counter cation is linked to an oxygen atom of a sulphonyl group by an enol type che1ati0n.l~ Therefore, an aldehyde approaching the reaction centre is OH OH Major Minor assumed to form a six-membered ring chelation system as shown in Scheme 5. Reaction as given in B might be suppressed due to steric repulsion between the alkyl group of an aldehyde and THF co-ordinating an alkoxide group, and the reaction from the other side at a reaction centre also be greatly suppressed owing to * We could separate all four diastereoisomers, which were obtained by another method, on an h.p.1.c.column and hence confirm that only two diastereoisomers were formed in the reaction of the dianion of (1). t The isolated products, major and minor (3b), were converted readily into acetonides and their configurations established on the basis of coupling constants in 400 MHz 'H n.m.r. spectra of acetonide. See, A. Hampton, J. Am. Chem. SOC.,1961,83,3640. 2400 J. CHEM. SOC. PERKIN TRANS. I 1988 OH Scheme 5. steric hindrance of an alkyl side chain R' of (1). Consequently, the reaction proceeds as shown in A to give the 1,3-synisomer as a major product.Experimental 'H N.m.r. spectra were recorded on JEOL Model PS-100(100 MHz) or JEOL Model JMN-FX 400(400MHz) instruments; chemical shifts (6) are expressed in p.p.m. relative to tetramethylsilane. 1.r. spectra were measured with a Hitachi Model 215 spectrometer. Mass spectra were recorded with a JEOL JMS-DX-300 spectrometer. H.p.1.c. analyses were carried out on a Shimadzu LC-6A system containing a 7125valve loop injector (Rheodyne, Berkeley, CA, USA), and an ODS column or a PYEcolumn in aqueous methanol. THF and ether were dried by standard techniques and distilled under argon. Commercial butyl-lithium in hexane was standardized by the method of Kofron.' Alkyl halides, aldehydes, and the additives were purified by standard tech- niques.Enantiomerically pure (2s)-1-phenylsulphonylpropan-2-01 (la) and other 1-phenylsulphonylalkan-2-01s(1b-d) were prepared using reported method^.'^,'^ General Procedure for Alkylation of (la-d).-Under an atmosphere of argon, BuLi (2.2mmol, 1.4~in hexane) was added dropwise to a solution of 1-phenylsulphonylalkan-2-ols (1) (1 mmol) in anhydrous THF at -78 OC, and the additive added as appropriate. The mixture was stirred for 30min, the alkyl halide was added dropwise, and the resulting solution was stirred for 30min at -78"C, allowed to warm to 20"C over 2h, and then quenched by addition of saturated aqueous NH4C1. The organic layer was separated and the aqueous layer was extracted twice with ethyl acetate.The organic phase was dried (Na,SO,), the solvents were evaporated off, and the products were isolated by column chromatography on silica gel (Wakogel C200) and/or h.p.lc. Monodeuteriated (lc). The alcohol (lc) was used as a sub- strate, oil; v,,,. (neat) 3500(OH), 2 900 (CH,), 1 320,and 1 150 cm-' (SO,); 6, (400MHz; CDCI,) 0.87(t, 3H, J 7.02 Hz), 1.23 (br s, 16H), 3.18(br s, 1 H), 3.42(s, 1 H), 4.11 (br s, 1 H), 7.56-7.69(m, 3 H), and 7.92-7.95 (m, 2H). Alkylating Reagents.-3- Phenylsulphonylbutan-2-01(2a).Mix-ture, viscous oil; v,,,.(neat) 3 500(OH), 3 100 (Ph), 1 300,and 1 150cm-' (SO,); 6, (100MHz; CDCI,) 1.28(d, 3H, J 6.5 Hz),1.32(d, 3H, J7.3Hz), 2.9(br s, 1 H), 3.0-3.28(m, 2H), 4.10-4.30(m, 1 H), 7.56-7.69(m, 3H), and 7.92-8.00 (m, 2H); m/z (relative intensity) 215 (M + 1, 2.3), 199 (M -CH,, 3579, and 170(M -C2H,0, 100).3-Phenylsulphonylpentan-2-01 (2b). Mixture, viscous oil; v,,,.(neat) 3 500 (OH), 2 950 (CH,), 1 310,and 1 160 cm-' (SO,); 6, (100MHz; CDCl,) 0.87(t, 3H, J 7.0 Hz), 1.24(d, 3H, J6.6Hz), 1.40-1.80 (m,2H), 2.80-3.20(m, 1 H), 3.6(br s, 1 H), 4.2W.60(m, 1 H), 7.40-7.62(m, 3H), and 7.80-8.00(m,2 H); m/z (relative intensity) 229 (M + 1, 2.4), 213 (M -CH,, 35), and 184(M -C2H40, 100).3-Phenylsulphonylundecan-2-01 (2c). Mixture, viscous oil; v,,,.(neat) 3500 (OH), 2 900 (CH,), 1 310,and 1 150 cm-' (SO,); 6, (100 MHz; CDCI,) 0.80--1.00(m, 6 H), 1.00-1.24(br s, 12H), 1.60-2.00 (m, 2H), 2.88(t, d, 1 H, J 5.8 and 2.4Hz),3.24(br s, 1 H), 4.2W.52(br s, 1 H), 7.40-7.68(m, 1 H), and 7.68-7.96 (m, 2H); m/z(relative intensity) 326(M+,0.7), 311 (M -CH,, 15), and 282(M -C,H40, 100).3-Phenyisulphonylhex-5-en-2-olerythro-(Zd).Viscous oil; v,,,,(neat) 3 500(OH), 1 640(CH,=CH), 1 300,and 1 150cm-' (SO,); 6,(100 MHz; CDCI,) 1.28(d, 3H, J6.5Hz), 2.57(t, 2H, J 7.1Hz), 2.96-3.24(br s, 1 H), 3.17(t, d, 1 H, J 5.8 and 2.4Hz),4.2W.48(m, 1 H), 4.84-5.08 (m, 2H), 5.40-5.76(m, 1 H), 7.4k7.72(m, 3 H), and 7.80-7.96 (m, 2 H); m/z (relative intensity) 241(M + 1, 3.0),240(M', 0.7), 225 (M -CH,, 2.3), 196 (M -C2H40,2.4),and 98(M -PhSO,H, 100).Compound threo-(2d), 6, (100MHz; CDCI,) 1.28(d, 3H, J 6.6 Hz), 2.53(t, 2H, J7.3Hz), 2.96-3.24(br s, 1 H), 3.22(t, d, 1 H, J 6.1and 6.1Hz), 4.2W.48(m, 1 H), 4.84-5.08 (m, 2H), 5.40-5.76(m, 1 H), 7.40-7.73(m, 3 H), and 7.80-7.96(m, 2H).6-Methyl-3-phenylsulphonylhept-5-en-2-ol(2e). Mixture, vis- cous oil; v,,,.(neat) 3500(OH), 2 900 (CH,), 1 640(CH,=CH),1 310,and 1 160cm-' (SO,); amp;,(lo0 MHz; CDCI,) 1.32(d, 3H, J 6.9 Hz), 1.52(d, 6H, J 5.9 Hz), 2.50(t, 2H, J 6.6 Hz), 3.00(t, d, 1 H, J 5.8 and 2.4Hz), 3.16(br s, 1 H), 4.20-4.60(m, 1 H), 4.80-5.00(m, 1 H), 7.40-7.66(m, 3H), and 7.80-8.00(m, 2H); m/z (relative intensity) 269(M + 1,373,268(M+,0.6), 253 (M -CH,, 2.4), 224 (M -C2H40, 2.5), and 154 (M -PhSO,H, 100). 5-Methyl-2-phenylsulphonylhexan-3-olerythro-(2f). Vis-cous oil; v,,,.(neat) 3 500(OH), 2 950 (CH,), 1 300,and 1 160 cm-' (SO,); 6,(400 MHz; CDCI,) 0.817(d, 3 H, J 6.71 Hz),0.854(d, 3H, J6.72),1.313(d, 3H, J7.01Hz), 1.513-1.585 (m, 2 H), 1.652-1.721 (m, 1 H), 2.870(br s, 1 H), 3.006(9, d, 1 H, J 7.02and 1.22Hz), 4.1 19 (9, J7.02Hz, 1 H), 7.571-7.708 (m,3 H), and 7.89Ck7.927(m, 2H); m/z(relative intensity) 257(M + 1,1.4), 256 (M+,2.3), 199 (M -C4H,, 17), and 170(M -CSH 100).Compound threo-(2f), 6,(400 MHz; CDC1,) 0.900(d, 3H, J6.41Hz), 0.932(d, 3H, J7.32Hz), 1.156(d, 3H, J 7.32Hz), 1.235-1.321 (m, 2H), 1.451-1.489 (m, 1 H), 3.096 3.208(m, 1 H), 3.682(br s, 1 H), 4.0924.145(m, 1 H), 7.556-7.707(m, 3 H), and 7.893-7.921 (m, 2H). 2-MethyI-5-phenylsulphonyloct-7-en-4-olerythro-(Zg). Vis- cous oil; v,,,.(neat) 3 500 (OH), 3 100(Ph), 2 900 (CH,), 1 640 (olefin), 1 300,and 1 150cm-' (SO,); 6, (100MHz; CDCI,) 0.62-1.02 (m, 6H), 1.02-1.40 (m, 1 H), 1.4-1.96 (m, 2H), 2.56 (t, 2H, J7.3Hz), 2.96-3.22(br s, 1 H), 3.15(t, d, 1 H, J5.8and 2.4Hz), 4.20-4.48(br s, 1 H), 4.84-5.20(m, 2H), 5.48-5.92 (m, 1 H), 7.48-7.80 (m, 3 H), and 7.80-8.08(m, 2 H); m/z (relative intensity) 283 (M + 1, 2.9), 282 (M+, 0.6), 225 (M -C4H9,3.0), 196(M -C,HloO, 3.2), and 140(M -PhSO,H, 100).Compound threo-(2g), 6,( 100 MHz; CDC1,)0.62-1.00 (m, 6H), 1.00-1.38(m, 1 H), 1.4k1.96(m, 2H), 2.48(t, 2H, J 7.2Hz), 3.00-3.25(br s, 1 H), 3.25(t, d, 1 H, J 6.1and 6.1Hz), 4.20-4.50(br s, 1 H), 4.84-5.20 (m, 2 H), J. CHEM. SOC. PERKIN TRANS. I 1988 5.48-6.00 (m, 1 H), 7.48-7.80 (m, 3 H), and 7.80-8.00 (m,2H). 3-Phenylsulphonyldodecan-2-01erythro-(2h). Viscous oil; v,,,.(neat) 3500 (OH), 2 950 (CH,), 1 310,and 1 150 cm-' (SO,); 6H(400 MHz; CDCI,) 0.874(t, 3H, J 7.02 Hz), 1.316(d, 3 H, J7.02Hz), 1.2261.626(m, 16H), 2.906(br s, 1 H), 3.037(q, d, 1 H, J 7.02 and 1.22Hz), 4.243(q, 1 H, J 3.97 Hz), 7.573-7.707 (m, 3 H), and 7.893-7.916 (m, 2 H); m/z (relative intensity) 326 (M+,0.7), 199 (M -C9HI9, 1273, and 170 (M -C10H200,100).Compound threo-(2h), 6,(400 MHz; CDCI,) 0.874(t, 3 H, J 7.02Hz), 1.156(d, 3 H, J 7.02 Hz),1.256-1.617(m, 16 H), 3.186(q, d, 1 H, J 7.33 and 7.02Hz),3.822(br s, 1 H), 3.9974.037(m, 1 H), 7.569-7.701 (m, 3H), and 7.894-7.918 (m, 2H). 5-Phenylsulphonyltetradec-1-en-4-01erythro-(2i). Viscous oil; v,,,,(neat) 3 500 (OH), 2 920 (CH,), 1640(olefin), 1 310, and 1 160cm-' (SO,); 6, (400MHz; CDCI,) 0.87(t, 3H, J 7.02 Hz), 1.22(br s, 16H), 2.61-2.69 (m, 2H), 3.15-3.19 (br s, 1 H),3.17(t, d, 1 H, J5.80and 2.44Hz), 4.02-4.32(m, 1 H), 4.92-5.16(m, 2 H), 5.52-5.92 (m, 1 H), 7.42-7.72 (m, 3 H), and 7.72-8.02 (m, 2H); m/z (relative intensity) 353(M + 1,2.8),352 (M+,0.8), 225 (M -C9H19, 2.3), and 210 (M -PhSO,H, looo,/,).Compound threu-(2i), 6,(400 MHz; CDCI,) 0.87(t, 3 H, J 7.02Hz), 1.25(m, 16 H), 2.41-2.51 (m,2 H),3.20-3.25(br s, 1 H), 3.22(t, d, 1 H, J6.10Hz), 4.024.42(m, 1 H), 4.92-5.16(m, 2H), 5.52-5.92 (m, 1 H), 7.42-7.72 (m, 3 H), and 7.72--8.03(m, 2H).4-Phen~~l-3-phen~~lsulphonylbutan-2-olerythro-(2j). Viscous oil; v,,,.(neat) 3 500 (OH), 3OOO (CH,), 1 460,1 310,and 1 160 cm-' (SO,); 6,(400 MHz; CDCl,) 1.383(d, J 7.02Hz, 3 H),2.429-2.642 (m, 2H), 2.80(br s, 1 H), 3.102(9, 1 H, J 7.33Hz), 4.101(4, 1 H,J 7.02Hz), and 7.109-7.912 (m, 10 H); m/z (relative intensity) 291 (M + 1, 0.4), 290 (M', 0.273, 199 (M -PhCH,, loo), and 170 (M -PhCH,CHO, 22).Compound threo-(6j), 6,(400 MHz; CDCl,) 1.289(d, 3 H, J 7.02Hz), 2.622--2.700(m, 2 H), 3.271(9, d, 1 H, J7.33and 7.02 Hz), and 7.190-7.916(m, 10H). 1-Phen~~l-2-phenylsulphonylhex-5-en-3-ol erythro-(2k). Viscous oil: v,,,.(neat) 3 500 (OH), 3 100 (Phj, 1640(olefin), 1 320,and I 160 cm-' (SO,); 6,(100 MHz; CDCI,) 2.50-2.70 (m, 4H),3.15--3.19(br s, 1 H), 3.17(t, d, 1 H, J5.8and 2.4Hz),4.024.42(br s, 1 H), 4.92-5.16 (m, 2H), 5.52-5.92 (m, 1 H), and 7.19--8.00(m, 10 H); m/z (relative intensity) 317(M + 1, 2.8",,),225 (M -PhCH,, 2.8), and 196 (M -PhSO,H, 1OO";,).Generul Procedurefi7r the Reaction uf the Dianion with Aldehydes.-The aldehyde (1.1 equiv.) was added at -78"C to the solution of dianion, prepared by the same method as in the alkylation reaction. After being stirred for 30min at -78"C the reaction was quenched by addition of saturated aqueous NH,Cl. The products were isolated by a similar work-up to that previously used. 3-Phenj~lsulphonyltridecane-2,4-diol(3a).Mixture, viscous oil; v,,,.(neat) 3 500 (OH), 2 900 (CH,), 1 590,1 310,and 1 150 cm-' (SO,); 6,( 100 MHz; CDCI,) 0.88 (t, 3H, J 7.0 Hz), 1.-1.80 (m, 19H), 3.08-3.20(m, 1 H), 3.4G3.80(br s, 2H), 4.00-4.60(m, 2H),7.40-7.76(m, 3H), and 7.78-8.00 (m, 2H); m/z (relative intensity) 357(M + 1, 1), 229(M -C9H19, loo),and 141 (PhSO,, 90).3-Phenj~lsulphonylpentadecane-2,4-diol(3b). Major isomer, Viscous oil; v,,,.(neat) 3500 (OH), 2900(CH,), 1 590,1 320, and 1 150 cm-' (SO,); 6, (100MHz; CDCI,) 0.88 (t, 3H, J 7.0 Hz), l.OQ--1.80(m, 23H), 3.063.20(m, 1 H), 3.40-3.80(br s, 2H), 4.0W.60(m, 2H), 7.40-7.76(m, 3 H), and 7.78-8.00 (m, 2H); m/z (relative intensity) 385(M + 1,0.8), 229 (M -C, 1H23,1000//,),and 141(PhSO,, 98).Compound (3b) (minor isomer), 6, (100 MHz; CDCI,) 0.88 (t, 3H, J 7.0 Hz), 1.00-1.80 2401 (m, 23H), 3.08-3.24 (m, 1 H), 3.40-3.80 (br s, 2H), 4.W.60 (m, 2H), 7.40-7.76(m, 3 H), and 7.78-8.00 (m, 2H). 6,1O-Dimethyl-3-phenylsulphonylundec-9-ene-2,4-diol (3c). Mixture, viscous oil; v,,,.(neat) 3 500 (OH), 2 950 (CH,), 1 320, and 1 160cm-' (SO,); amp;,(lo0 MHz; CDCI,) 0.82(d, 3 H, J 6.6 Hz), 1.00-2.00(m, 19H), 3.08-3.20 (m, 1 H), 3.40-3.80(br s, 2H), 4.00-4.60 (m, 2H), 5.00 (t, 1 H, J6.6Hz), 7.40-7.76(m, 3 H), and 7.78-8.00 (m, 2H); m/z (relative intensity) 355(M + 1, 1), 229(M -C9H17, loo), and 141(PhSO,, 90).2-Methyl-5-phenylsulphonylpentadecane-4,6-diol(3d). Mix-ture, viscous oil; v,,,.(neat) 3500 (OH), 2 900 (CH,), 1 310, and 1 160cm-' (SO,); 6,(100 MHz; CDCI,) 0.76-1.00(m, 9H), 1.G1.80 (m, 18 H), 3.08(m, 1 H), 3.70(br s, 2H), 4.06-4.48 (m,2 H), 7.40-7.68 (m, 3 H), and 7.68-7.96 (m, 2 H); m/z (relative intensity) 399(M + 1, 1), 271(M -C9H19, loo),and 141 (PhSO,, 95). 2-Methyl-5-phenylsulphonylheptadecane-4,6-diol(3e).Mix-ture, viscous oil; v,,,.(neat) 3500(OH), 2 900 (CH,), 1 310,and 1 150 cm-' (SO,); 6,(100 MHz; CDCl,) 0.761.00(m, 9H),1.00-1.80(m, 22H), 3.08(m, 1 H), 3.70(br s, 2H), 4.06-4.48 (m, 2 H), 7.40-7.68(m, 3 H), and 7.68-7.96 (m, 2 H); m/z (relative intensity) 413(M + 1, 1), 271 (M -C, 1H23, 90), and 141(PhSO,, 1000/0). 2,8,12-Trimethyl-5-phenylsulphonyltridec-11-ene-4,6-diol(3f). Mixture, viscous oil; v,,,.(neat) 3 500(OH), 2900 (CH,), 1 320, and 1 150 cm-' (SO,); 6,(100 MHz; CDCI,) 0.76-1.00 (m, 9 H), 1.00-2.00(m, 17H), 3.08(m, 1 H), 3.70(br s, 2H), 4.06 4.48(m, 2H), 5.00(t, 1 H,J6.6Hz), 7.4G7.68(m,3 H),and 7.68-7.96 (m, 2H); m/z (relative intensity) 397(M + 1, l",),271 (M -C9H17, loo), and 141 (PhSO,, 95).5-Phenylsulphonylpen tadecane-4,6-diol (3g). Major isomer, viscous oil; v,,,.(neat) 3500 (OH), 2 900 (CH,), 1 310br, and 1 150br cm-' (SO,); amp;,(lo0 MHz; CDCI,) 0.66-1.06(m, 6H),1.06-2.00 (m, 20H), 3.06-3.20(m, 1 H), 3.66(m, 2H), 4.06-4.46(m, 2H), 7.40-7.80(m, 3H), and 7.80-8.00(m, 2H); mjz (relative intensity) 271 (M -C9H19, 90) and 141 (PhSO,, 100). Compound (3g)(minor isomer), 6,( 100 MHz; CDCl,) 0.70-1.00(m, 6H), 1.00-1.86(m, 20H), 3.08--3.24(m, 1 H),3.24-3.72 (br s, 2H), 4.0M.40(m, 2H), 7.40-7.78(m, 3H), and 7.78-8.00 (m, 2H). Acknowledgements The present work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science and Culture. References 1 Parts of this work have been previously published as a preliminary communication. See, R.Tanikaga, K. Hosoya, K. Hamamura, and A. Kaji, Tetrahedron Lett., 1987, 28, 3705. 2 M. Hatanaka and N. Nitta, Tetrahedron Lett., 1987,28,69, and 1987, 28, 83. 3 G. W. Klumpp, Reel. Trau. Chim. Pay-Bas., 1986, 105, 1. 4 K. Tanaka and A. Kaji, 'The Synthetic Utility of Sulfur-containing Dianions' in 'Sulfur Report,' ed. A. Senning, Harwood (U.S.A.), 1980. 5 B.-T. Grobel and D. Seebach, Synthesis, 1977, 357. 6 D. Seebach, Angew. Chem., Int. Ed. Engl., 1979, 18, 239. 7 P. C. Conrad and P. L. Fuchs, J. Am. Chem. SOC.,1978, 100, 346. 8 J. C.Saddler, P. C. Conrad, and P. L. Fuchs, Tetrahedron Lett., 1978, 507. 9 R. Tanikaga, K. Hosoya, and A. Kaji, J. Chem. Soc.. Perkin Trans. 1, 1987, 1799. 10 R. Tanikaga, K. Hosoya, and A. Kaji, Synthesis, 1987, 389. 11 A. P. Kozikowski, B. B. Mugrage, C. S. Li, and L. Felder, Tetrahedron Lett., 1986, 27, 4817. 12 K. Tanaka, K. Ohtake, K. Imai, N. Tanaka, and A. Kaji, Chem. Lett., 1983, 633. 2402 J. CHEM. SOC. PERKIN TRANS. I 1988 13 D. Barr, W. Clegg, R. E. Mulvey, R. Snaith, and W. S. Wright, J. 17 N. Tanaka, Y. Tokuda, K. Iwaguchi, and M. Araki, J. Chromatogr., Chem. Soc. Chem. Commun., 1987, 716. 1982, 239, 761. 14 C. Reichardt, lsquo;Solvent Effects in Organic Chemistry,rsquo; Verlag Chemie, 18 W. G. Kofron and L. Baclainski, J. Org. Chem., 1976, 41, 451. Weinheim, 1979. 19 S. Iriuchijima and N. Kojima, Agric. Biol. Chem., 1978, 42, 451. 15 H.-J. Gais, J. Vollhardt, and H. J. Linder, Angew. Chem., Znt. Ed. Enamp; 1986, 25, 939. 16 R. Strazewski and C. Tamm, ffelu. Chim. Acta., 1986, 69, 1041. Received 13th November 1987; Paper 7/2014
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