Nicolaou KC, Li Y, Uesaka N, Koftis Television, Vyskocil S, Ling T, Govindasamy M, Qian W, Bernal F, Chen DY-K. attained regioselective epoxide band opportunities of ,-epoxy-,-unsaturated esters 15 and 16 with Ti(O-configuration of alkene 21 was verified with the 1H NMR range, which ultimately shows correlated two doublets ( 6.20 ppm, = 9.8 Hz, =C= 9.8 Hz, RCHCisomerization,27-30 it would appear that azide anion may play an identical function as pyridine inside our reaction. Reduced amount of an azide for an amine in the current presence of a dual bond isn’t trivial. Both Staudinger decrease (Ph3P, THF/H2O) and 1,3-propanedithiol/Et3N31 didn’t produce satisfactory outcomes. Decrease using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 led to saturation from the dual bond. Thankfully, as illustrated in System 4, we discovered that simultaneous reduced amount of the azide and demethylation of methyl ester 17 was achieved by using SnCl2in 95% MeOH,33 offering 2 in 69% produce, as well as 22 (17% produce). Methyl ester 22 was changed to 2 by treatment with TMSBr in quantitative produce. Our new artificial path to 2 includes nine techniques from commercially obtainable aldehyde 8 in 19% general produce. The azide analogue 5 was produced by demethylation of 17 with TMSBr, accompanied by aqueous MeOH, within a quantitative produce. The stereochemistry of 22 was verified by its particular rotation: []25D +20.0 (0.18, CHCl3) [lit.5 []25D +18.8 (1.52, CHCl3)]. Open up in another window System 4 Synthesis of 2 and 5. Fluorination of 17 with DAST34 (?78 C, overnight, and at rt for 3 h) produced 23 in 75% yield (System 4). Termination from the response at low heat range led to imperfect conversion. As opposed to 17, reduced amount of A-1155463 23 using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 didn’t reduce the dual bond, offering 24 in 51% produce. Demethylation of methyl esters 23 and 24 with TMSBr accompanied by 95% MeOH afforded the mark fluorine-containing analogues 4 and 3, respectively, in quantitative produces. The unsaturated carboxylic acidity analogue 6 was made by reduced amount of 20 (SnCl2 in MeOH), accompanied by hydrolysis of ester 25 with LiOH in THF/MeOH/H2O. Catalytic hydrogenation of 21 (H2, Pd/C) supplied lactone analogue 7 in 46% produce. 3. Biological evaluation We’ve shown that = 7.8 Hz, 2H), 2.72 (t, = 8.2 Hz, 2H), 2.99 (d, = 4.6 Hz, 1H), 3.04 (d, = 4.6 Hz, 1H), 7.10-7.13 (m, 4H), 8.89 (s, 1H); 13C NMR (125 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.5, 29.9, 30.2, 31.5, 31.9, 35.5, 49.8, 60.9, 128.1, 128.5, 138.0, 140.8, 198.8; ESI-HRMS (M+Na)+ calcd for C19H28NaO2+ 311.1982, found 311.1986. 5.1.5. Planning of (= 5.4 Hz, 1H), 3.72 (d, = 5.5 Hz, 3H), 3.74 (d, = 5.5 Hz, 3H), 5.95 (dd, = 17.2, 19.4 Hz, 1H), 6.83 (dd, = 17.2, 22.2 Hz, 1H), 7.05-7.13 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.4, 30.6, 31.5, 31.8, 35.2, 35.5, 52.38 (d, = 5.4 Hz), 52.41 (d, = 5.4 Hz), 55.9, 58.2 (d, = 24.0 Hz), 116.5 (d, = 189.6 Hz), 128.0, 128.5, 137.9, 140.8, 151.6 (d, = 6.5 Hz); 31P NMR (162 MHz, CDCl3) 20.6; ESI-HRMS (M+H)+ calcd for C22H36O4P+ 395.2346, found 395.2346. 5.1.6. Planning of (= 7.7 Hz, 2H), 2.65-2.75 (m, 3H), 2.88 (d, = 5.4 Hz, 1H), 4.21 (q, = 7.1 Hz, 2H), 6.10 (d, = 15.7 Hz, 1H), 6.91 (d, = 15.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 14.2, 22.6, 29.2, 29.3, 29.5, 30.7, 31.5, 31.9, 35.45, 35.52, 55.8, 57.6, 60.6, 122.2, 128.1, 128.5, 138.1, 140.8, 146.6, 166.0; ESI-HRMS (M+Na)+ calcd for C23H34NaO3+ 381.2400, found 381.2401. 5.1.7. Planning of (= 17.1, 19.3 Hz, 1H), 6.72 (dd, = 17.2, 22.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.46, 29.50, 31.6, 31.9, 35.5, 36.0, 52.53 (d, = 5.5 Hz), 52.55 (d, = 5.5 Hz), 67.4, 69.0 (d, = 19.4 Hz), 118.1 (d, = 186.9 Hz), 128.1, 128.6, 137.9, 140.9, 151.0 (d, = 6.3 Hz); 31P NMR (162 MHz, CDCl3) 20.5; ESI-HRMS (M+H)+ calcd for C22H36N3O4P+ 438.2516, found 438.2519..[Google Scholar] 13. few organized research on ring-opening reactions of vinyl epoxides by azide ion have already been released.19-23 We achieved regioselective epoxide band openings of ,-epoxy-,-unsaturated esters 15 and 16 with Ti(O-configuration of alkene 21 was verified with the 1H NMR spectrum, which ultimately shows correlated two doublets ( 6.20 ppm, = 9.8 Hz, =C= 9.8 Hz, RCHCisomerization,27-30 it would appear that azide anion might enjoy an identical role as pyridine inside our reaction. Reduced amount of an azide for an amine in the current presence of a dual bond isn’t trivial. Both Staudinger decrease (Ph3P, THF/H2O) and 1,3-propanedithiol/Et3N31 didn’t produce satisfactory outcomes. Decrease using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 led to saturation from the dual bond. Thankfully, as illustrated in System 4, we discovered that simultaneous reduced amount of the azide and demethylation of methyl ester 17 was achieved by using SnCl2in 95% MeOH,33 offering 2 in 69% produce, as well as 22 (17% produce). Methyl ester 22 was changed to 2 by treatment with TMSBr in quantitative produce. Our new artificial path to 2 includes nine techniques from commercially obtainable aldehyde 8 in 19% general produce. The azide analogue 5 was produced by demethylation of 17 with TMSBr, accompanied by aqueous MeOH, within a quantitative produce. The stereochemistry of 22 was verified by its particular rotation: []25D +20.0 (0.18, CHCl3) [lit.5 []25D +18.8 (1.52, CHCl3)]. Open up in another window System 4 Synthesis of 2 and 5. Fluorination of 17 with A-1155463 DAST34 (?78 C, overnight, and at rt for 3 h) produced 23 in 75% yield (System 4). Termination from the response at low heat range led to imperfect conversion. As opposed to 17, reduced amount of 23 using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 didn’t reduce the dual bond, offering 24 in 51% produce. Demethylation of methyl esters 23 and 24 with TMSBr accompanied by 95% MeOH afforded the mark fluorine-containing analogues 4 and 3, respectively, in quantitative produces. The unsaturated carboxylic acidity analogue 6 was made by reduced amount of 20 (SnCl2 in MeOH), accompanied by hydrolysis of ester 25 with LiOH in THF/MeOH/H2O. Catalytic hydrogenation of 21 (H2, Pd/C) supplied lactone analogue 7 in 46% produce. 3. Biological evaluation We’ve previously proven that = 7.8 Hz, 2H), 2.72 (t, = 8.2 Hz, 2H), 2.99 (d, = 4.6 Hz, 1H), 3.04 (d, = 4.6 Hz, 1H), 7.10-7.13 (m, 4H), 8.89 (s, 1H); 13C NMR (125 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.5, 29.9, 30.2, 31.5, 31.9, 35.5, 49.8, 60.9, 128.1, 128.5, 138.0, 140.8, 198.8; ESI-HRMS (M+Na)+ calcd for C19H28NaO2+ 311.1982, found 311.1986. 5.1.5. Planning of (= 5.4 Hz, 1H), 3.72 (d, = 5.5 Hz, 3H), 3.74 (d, = 5.5 Hz, 3H), 5.95 (dd, = 17.2, 19.4 Hz, 1H), 6.83 (dd, = 17.2, 22.2 Hz, 1H), 7.05-7.13 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.4, 30.6, 31.5, 31.8, 35.2, 35.5, 52.38 (d, = 5.4 Hz), 52.41 (d, = 5.4 Hz), 55.9, 58.2 (d, = 24.0 Hz), 116.5 (d, = 189.6 Hz), 128.0, 128.5, 137.9, 140.8, 151.6 (d, = 6.5 Hz); 31P NMR (162 MHz, CDCl3) 20.6; ESI-HRMS (M+H)+ calcd for C22H36O4P+ 395.2346, found 395.2346. 5.1.6. Planning of (= 7.7 Hz, 2H), 2.65-2.75 (m, 3H), 2.88 (d, = 5.4 Hz, 1H), 4.21 (q, = 7.1 Hz, 2H), 6.10 (d, = 15.7 Hz, 1H), 6.91 (d, = 15.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) .Angew. was verified with the 1H NMR range, which ultimately shows correlated two doublets ( 6.20 ppm, = 9.8 Hz, =C= 9.8 Hz, RCHCisomerization,27-30 it would appear that azide anion might enjoy an identical role as pyridine inside our reaction. Reduced amount of an azide for an amine in the current presence of a dual bond isn’t trivial. Both Staudinger decrease (Ph3P, THF/H2O) and 1,3-propanedithiol/Et3N31 didn’t produce satisfactory outcomes. Decrease using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 led to saturation from the dual bond. Thankfully, as illustrated in System 4, we discovered that simultaneous reduced amount of the azide and demethylation of methyl ester 17 was achieved by using SnCl2in 95% MeOH,33 offering 2 in 69% produce, as well as 22 (17% produce). Methyl ester 22 was transformed to 2 by treatment with TMSBr in quantitative yield. Our new synthetic route to 2 consists of nine actions from commercially available aldehyde 8 in 19% overall yield. The azide analogue 5 was created by demethylation of 17 with TMSBr, followed by aqueous MeOH, in a quantitative yield. The stereochemistry of 22 was confirmed by its specific rotation: []25D +20.0 (0.18, CHCl3) [lit.5 []25D +18.8 (1.52, CHCl3)]. Open in a separate window Plan 4 Synthesis of 2 and 5. Fluorination of 17 with DAST34 (?78 C, overnight, and then at rt for 3 h) produced 23 in 75% yield (Plan 4). Termination of the reaction at low heat led to incomplete conversion. In contrast to 17, reduction of 23 using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 did not reduce the double bond, providing 24 in 51% yield. Demethylation of methyl esters 23 and 24 with TMSBr followed by 95% MeOH afforded the target fluorine-containing analogues 4 A-1155463 and 3, respectively, in quantitative yields. The unsaturated carboxylic acid analogue 6 was prepared by reduction of 20 (SnCl2 in MeOH), followed by hydrolysis of ester 25 with LiOH in THF/MeOH/H2O. Catalytic hydrogenation of 21 (H2, Pd/C) provided lactone analogue 7 in 46% yield. 3. Biological evaluation We have previously shown that = 7.8 Hz, 2H), 2.72 (t, = 8.2 Hz, 2H), 2.99 (d, = 4.6 Hz, 1H), 3.04 (d, = 4.6 Hz, 1H), 7.10-7.13 (m, 4H), 8.89 (s, 1H); 13C NMR (125 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.5, 29.9, 30.2, 31.5, 31.9, 35.5, 49.8, 60.9, 128.1, 128.5, 138.0, 140.8, 198.8; ESI-HRMS (M+Na)+ calcd for C19H28NaO2+ 311.1982, found 311.1986. 5.1.5. Preparation of (= 5.4 Hz, 1H), 3.72 (d, = 5.5 Hz, 3H), 3.74 (d, = 5.5 Hz, 3H), 5.95 (dd, = 17.2, 19.4 Hz, 1H), 6.83 (dd, = 17.2, 22.2 Hz, 1H), 7.05-7.13 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.4, 30.6, 31.5, 31.8, 35.2, 35.5, 52.38 (d, = 5.4 Hz), 52.41 (d, = 5.4 Hz), 55.9, 58.2 (d, = 24.0 Hz), 116.5 (d, = 189.6 Hz), 128.0, 128.5, Rabbit Polyclonal to PPIF 137.9, 140.8, 151.6 (d, = 6.5 Hz); 31P NMR (162 MHz, CDCl3) 20.6; ESI-HRMS (M+H)+ calcd for C22H36O4P+ 395.2346, found 395.2346. 5.1.6. Preparation of (= 7.7 Hz, 2H), 2.65-2.75 (m, 3H), 2.88 (d, = 5.4 Hz, 1H), 4.21 (q, = 7.1 Hz, 2H), 6.10 (d, = 15.7 Hz, 1H), 6.91 (d, = 15.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 14.2, 22.6, 29.2, 29.3, 29.5, 30.7, 31.5, 31.9, 35.45, 35.52, 55.8, 57.6, 60.6, 122.2, 128.1, 128.5, 138.1, 140.8, 146.6, 166.0; ESI-HRMS (M+Na)+ calcd for C23H34NaO3+ 381.2400, found 381.2401. 5.1.7. Preparation of (= 17.1, 19.3 Hz, 1H), 6.72 (dd, = 17.2, 22.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.46, 29.50, 31.6, 31.9, 35.5, 36.0, 52.53 (d, = 5.5 Hz), 52.55 (d, = 5.5 Hz), 67.4, 69.0 (d, = 19.4 Hz), 118.1 (d, = 186.9 Hz), 128.1, 128.6, 137.9, 140.9, 151.0.Bayley H, Standring DN, Knowles JR. and only a few systematic studies on ring-opening reactions of vinyl epoxides by azide ion have been published.19-23 We achieved regioselective epoxide ring openings of ,-epoxy-,-unsaturated esters 15 and 16 with Ti(O-configuration of alkene 21 was confirmed by the 1H NMR spectrum, which shows correlated two doublets ( 6.20 ppm, = 9.8 Hz, =C= 9.8 Hz, RCHCisomerization,27-30 it appears that azide anion might A-1155463 play a similar role as pyridine in our reaction. Reduction of an azide to an amine in the presence of a double bond is not trivial. Both Staudinger reduction (Ph3P, THF/H2O) and 1,3-propanedithiol/Et3N31 failed to produce satisfactory results. Reduction using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 resulted in saturation of the A-1155463 double bond. Fortunately, as illustrated in Plan 4, we found that simultaneous reduction of the azide and demethylation of methyl ester 17 was accomplished by using SnCl2in 95% MeOH,33 providing 2 in 69% yield, together with 22 (17% yield). Methyl ester 22 was transformed to 2 by treatment with TMSBr in quantitative yield. Our new synthetic route to 2 consists of nine actions from commercially available aldehyde 8 in 19% overall yield. The azide analogue 5 was created by demethylation of 17 with TMSBr, followed by aqueous MeOH, in a quantitative yield. The stereochemistry of 22 was confirmed by its specific rotation: []25D +20.0 (0.18, CHCl3) [lit.5 []25D +18.8 (1.52, CHCl3)]. Open in a separate window Plan 4 Synthesis of 2 and 5. Fluorination of 17 with DAST34 (?78 C, overnight, and then at rt for 3 h) produced 23 in 75% yield (Plan 4). Termination of the reaction at low heat led to incomplete conversion. In contrast to 17, reduction of 23 using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 did not reduce the double bond, providing 24 in 51% yield. Demethylation of methyl esters 23 and 24 with TMSBr followed by 95% MeOH afforded the target fluorine-containing analogues 4 and 3, respectively, in quantitative yields. The unsaturated carboxylic acid analogue 6 was prepared by reduction of 20 (SnCl2 in MeOH), followed by hydrolysis of ester 25 with LiOH in THF/MeOH/H2O. Catalytic hydrogenation of 21 (H2, Pd/C) provided lactone analogue 7 in 46% yield. 3. Biological evaluation We have previously shown that = 7.8 Hz, 2H), 2.72 (t, = 8.2 Hz, 2H), 2.99 (d, = 4.6 Hz, 1H), 3.04 (d, = 4.6 Hz, 1H), 7.10-7.13 (m, 4H), 8.89 (s, 1H); 13C NMR (125 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.5, 29.9, 30.2, 31.5, 31.9, 35.5, 49.8, 60.9, 128.1, 128.5, 138.0, 140.8, 198.8; ESI-HRMS (M+Na)+ calcd for C19H28NaO2+ 311.1982, found 311.1986. 5.1.5. Preparation of (= 5.4 Hz, 1H), 3.72 (d, = 5.5 Hz, 3H), 3.74 (d, = 5.5 Hz, 3H), 5.95 (dd, = 17.2, 19.4 Hz, 1H), 6.83 (dd, = 17.2, 22.2 Hz, 1H), 7.05-7.13 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.4, 30.6, 31.5, 31.8, 35.2, 35.5, 52.38 (d, = 5.4 Hz), 52.41 (d, = 5.4 Hz), 55.9, 58.2 (d, = 24.0 Hz), 116.5 (d, = 189.6 Hz), 128.0, 128.5, 137.9, 140.8, 151.6 (d, = 6.5 Hz); 31P NMR (162 MHz, CDCl3) 20.6; ESI-HRMS (M+H)+ calcd for C22H36O4P+ 395.2346, found 395.2346. 5.1.6. Preparation of (= 7.7 Hz, 2H), 2.65-2.75 (m, 3H), 2.88 (d, = 5.4 Hz, 1H), 4.21 (q, = 7.1 Hz, 2H), 6.10 (d, = 15.7 Hz, 1H), 6.91 (d, = 15.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz,.J. no additional stabilizing group is present, a [3,3]-sigmatropic equilibration process takes place to create a mixture of regioisomers. Therefore, this reaction is of little value,19 and only a few systematic studies on ring-opening reactions of vinyl epoxides by azide ion have been published.19-23 We achieved regioselective epoxide ring openings of ,-epoxy-,-unsaturated esters 15 and 16 with Ti(O-configuration of alkene 21 was confirmed by the 1H NMR spectrum, which shows correlated two doublets ( 6.20 ppm, = 9.8 Hz, =C= 9.8 Hz, RCHCisomerization,27-30 it appears that azide anion might play a similar role as pyridine in our reaction. Reduction of an azide to an amine in the presence of a double bond is not trivial. Both Staudinger reduction (Ph3P, THF/H2O) and 1,3-propanedithiol/Et3N31 failed to produce satisfactory results. Reduction using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 resulted in saturation of the double bond. Fortunately, as illustrated in Plan 4, we found that simultaneous reduction of the azide and demethylation of methyl ester 17 was accomplished by using SnCl2in 95% MeOH,33 providing 2 in 69% yield, together with 22 (17% yield). Methyl ester 22 was transformed to 2 by treatment with TMSBr in quantitative yield. Our new synthetic route to 2 consists of nine actions from commercially available aldehyde 8 in 19% overall yield. The azide analogue 5 was created by demethylation of 17 with TMSBr, followed by aqueous MeOH, in a quantitative yield. The stereochemistry of 22 was confirmed by its specific rotation: []25D +20.0 (0.18, CHCl3) [lit.5 []25D +18.8 (1.52, CHCl3)]. Open in a separate window Plan 4 Synthesis of 2 and 5. Fluorination of 17 with DAST34 (?78 C, overnight, and then at rt for 3 h) produced 23 in 75% yield (Plan 4). Termination of the reaction at low heat led to incomplete conversion. In contrast to 17, reduction of 23 using Lindlars catalyst (H2, Pd/CaCO3, EtOH)32 did not reduce the double bond, providing 24 in 51% yield. Demethylation of methyl esters 23 and 24 with TMSBr followed by 95% MeOH afforded the target fluorine-containing analogues 4 and 3, respectively, in quantitative yields. The unsaturated carboxylic acid analogue 6 was prepared by reduction of 20 (SnCl2 in MeOH), followed by hydrolysis of ester 25 with LiOH in THF/MeOH/H2O. Catalytic hydrogenation of 21 (H2, Pd/C) provided lactone analogue 7 in 46% yield. 3. Biological evaluation We have previously shown that = 7.8 Hz, 2H), 2.72 (t, = 8.2 Hz, 2H), 2.99 (d, = 4.6 Hz, 1H), 3.04 (d, = 4.6 Hz, 1H), 7.10-7.13 (m, 4H), 8.89 (s, 1H); 13C NMR (125 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.5, 29.9, 30.2, 31.5, 31.9, 35.5, 49.8, 60.9, 128.1, 128.5, 138.0, 140.8, 198.8; ESI-HRMS (M+Na)+ calcd for C19H28NaO2+ 311.1982, found 311.1986. 5.1.5. Preparation of (= 5.4 Hz, 1H), 3.72 (d, = 5.5 Hz, 3H), 3.74 (d, = 5.5 Hz, 3H), 5.95 (dd, = 17.2, 19.4 Hz, 1H), 6.83 (dd, = 17.2, 22.2 Hz, 1H), 7.05-7.13 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.4, 30.6, 31.5, 31.8, 35.2, 35.5, 52.38 (d, = 5.4 Hz), 52.41 (d, = 5.4 Hz), 55.9, 58.2 (d, = 24.0 Hz), 116.5 (d, = 189.6 Hz), 128.0, 128.5, 137.9, 140.8, 151.6 (d, = 6.5 Hz); 31P NMR (162 MHz, CDCl3) 20.6; ESI-HRMS (M+H)+ calcd for C22H36O4P+ 395.2346, found 395.2346. 5.1.6. Preparation of (= 7.7 Hz, 2H), 2.65-2.75 (m, 3H), 2.88 (d, = 5.4 Hz, 1H), 4.21 (q, = 7.1 Hz, 2H), 6.10 (d, = 15.7 Hz, 1H), 6.91 (d, = 15.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 14.2, 22.6, 29.2, 29.3, 29.5, 30.7, 31.5, 31.9, 35.45, 35.52, 55.8, 57.6, 60.6, 122.2, 128.1, 128.5, 138.1, 140.8, 146.6, 166.0; ESI-HRMS (M+Na)+ calcd for C23H34NaO3+ 381.2400, found 381.2401. 5.1.7. Preparation of (= 17.1, 19.3 Hz, 1H), 6.72 (dd, = 17.2, 22.7 Hz, 1H), 7.06-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.2, 29.3, 29.46, 29.50, 31.6, 31.9, 35.5, 36.0, 52.53 (d, = 5.5 Hz), 52.55 (d, = 5.5 Hz), 67.4, 69.0 (d, = 19.4 Hz), 118.1 (d, = 186.9 Hz), 128.1, 128.6, 137.9, 140.9, 151.0 (d, = 6.3 Hz); 31P NMR (162 MHz, CDCl3) 20.5; ESI-HRMS (M+H)+ calcd for C22H36N3O4P+ 438.2516, found 438.2519. 5.1.8. Preparation of (= 2.4, 11.1 Hz, 6H), 6.10 (dd, = 17.1, 20.3 Hz, 1H), 6.78 (dd, = 17.1, 22.3 Hz, 1H), 7.04-7.12 (m, 4H); 13C NMR (100 MHz, CDCl3) 14.1, 22.6, 29.0, 29.2, 29.3, 29.4, 31.5, 31.8, 35.5, 39.3, 52.46 (d, = 5.6 Hz), 52.49 (d, = 5.6.

Nicolaou KC, Li Y, Uesaka N, Koftis Television, Vyskocil S, Ling T, Govindasamy M, Qian W, Bernal F, Chen DY-K