Development of the First Brønsted Acid Assisted Enantioselective Brønsted Acid Catalyzed Direct Mannich Reaction

Abstract

We here describe the development of the first enantioselective Brønsted acid assisted chiral Brønsted acid catalyzed direct Mannich reaction of acetophenone with various aldimines. The reaction proceeds in the presence of a chiral and an achiral Brønsted acid which simultaneously activate the ketone and aldimine to give the corresponding β-amino ketones with good enantioselectivities and without the necessity of enolate preformation.

Key words

Mannich reaction - organocatalysis - Brønsted acid - BINOL-phosphate - cooperative catalysis

References and Notes

• For reviews:
• 1a Kobayashi S. Ishitani H. Chem. Rev.  1999,  99:  1069 
• 1b Kleinmann EF. In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.893 
• 1c Arend M. Westermann B. Risch N. Angew. Chem. Int. Ed.  1998,  37:  1045 
• 1d Arend M. Angew. Chem. Int. Ed.  1999,  38:  2873 
• 1e Cordova A. Acc. Chem. Res.  2004,  37:  102 
• 2a Fujieda H. Kanai M. Kambara T. Iida A. Tomioka K. J. Am. Chem. Soc.  1997,  119:  2060 
• 2b Ishitani H. Ueno M. Kobayashi S. J. Am. Chem. Soc.  1997,  119:  7153 
• 2c Kobayashi S. Ishitani H. Ueno M. J. Am. Chem. Soc.  1998,  120:  431 
• 2d Ishitani H. Ueno M. Kobayashi S. J. Am. Chem. Soc.  2000,  122:  8180 
• 2e Kobayashi S. Kobayashi J. Ishitani H. Ueno M. Chem. Eur. J.  2002,  8:  4185 
• 2f Hagiwara E. Fujii A. Sodeoka M. J. Am. Chem. Soc.  1998,  120:  2474 
• 2g Fujii A. Hagiwara E. Sodeoka M. J. Am. Chem. Soc.  1999,  121:  5450 
• 2h Ferraris D. Young B. Dudding T. Lectka T. J. Am. Chem. Soc.  1998,  120:  4548 
• 2i Ferraris D. Young B. Cox C. Drury WJ. Dudding T. Lectka T. J. Org. Chem.  1998,  63:  6090 
• 2j Ferraris D. Dudding T. Young B. Drury WJ. Lectka T. J. Org. Chem.  1999,  64:  2168 
• 2k Ferraris D. Young B. Cox C. Dudding T. Drury WJ. Ryzhkov L. Taggi AE. Lectka T. J. Am. Chem. Soc.  2002,  124:  67 
• For examples of Lewis acid catalyzed direct Mannich reactions, see:
• 3a Yamasaki S. Iida T. Shibasaki M. Tetrahedron Lett.  1999,  40:  307 
• 3b Yamasaki S. Iida T. Shibasaki M. Tetrahedron  1999,  55:  8857 
• 3c Matsunaga S. Kumagai N. Harada S. Shibasaki M. J. Am. Chem. Soc.  2003,  125:  4712 
• 3d Trost BM. Terrell LR. J. Am. Chem. Soc.  2003,  125:  338 
• 3e Juhl K. Gathergood N. Jørgensen KA. Angew. Chem. Int. Ed.  2001,  40:  2995 ; Angew. Chem. 2001, 113, 3083
• 3f Bernardi L. Gothelf AS. Hazell RG. Jørgensen KA. J. Org. Chem.  2003,  68:  2583 
• 3g Hamashima Y. Sasamoto N. Hotta D. Somei H. Umebayashi N. Sodeoka M. Angew. Chem. Int. Ed.  2005,  44:  1525 ; Angew. Chem. 2005, 117, 1549
• For Lewis base catalyzed enantioselective Mannich, see, for example:
• 4a List B. J. Am. Chem. Soc.  2000,  122:  9336 
• 4b Sakthivel K. Notz W. Bui T. Barbas CF. J. Am. Chem. Soc.  2001,  123:  5260 
• 4c Notz W. Sakthivel K. Bui T. Zhong G. Barbas CF. Tetrahedron Lett.  2001,  42:  199 
• 4d List B. Pojarliev P. Biller WT. Martin HJ. J. Am. Chem. Soc.  2002,  124:  827 
• 4e Cordova A. Notz W. Zhong G. Betancort JM. Barbas CF. J. Am. Chem. Soc.  2002,  124:  1842 
• 4f Cordova A. Barbas CF. Tetrahedron Lett.  2002,  43:  7749 
• 4g Watanabe S. Cordova A. Tanaka F. Barbas CF. Org. Lett.  2002,  4:  4519 
• 4h Cordova A. Watanaba S. Tanaka F. Notz W. Barbas CF. J. Am. Chem. Soc.  2002,  124:  1866 
• 4i Cordova A. Barbas CF. Tetrahedron Lett.  2003,  44:  1923 
• 4j Hayashi Y. Tsuboi W. Shoji M. Suzuki N. J. Am. Chem. Soc.  2003,  125:  11208 
• 4k Hayashi Y. Tsuboi W. Ashimine I. Urushima T. Shoji M. Sakai K. Angew. Chem. Int. Ed.  2003,  42:  3677 
• 4l Itoh T. Yokoya M. Miyauchi K. Nagata K. Oshawa A. Org. Lett.  2003,  5:  4301 
• 4m Notz W. Tanaka F. Watanabe S.-i. Chowdari NS. Turner JM. Thayumanavan R. Barbas CF. J. Org. Chem.  2003,  68:  9624 
• 4n Cobb AJA. Shaw DM. Ley SV. Synlett  2004,  558 
• 4o Ibrahem I. Casas J. Cordova A. Angew. Chem. Int. Ed.  2004,  43:  6528 
• 4p Westermann B. Neuhaus C. Angew. Chem. Int. Ed.  2005,  44:  4077 
• 4q Enders D. Grondal C. Vrettou M. Raabe G. Angew. Chem. Int. Ed.  2005,  44:  4079 
• 4r Lou S. Taoka BM. Ting A. Schaus SE. J. Am. Chem. Soc.  2005,  127:  11256 
• 4s Poulsen TB. Alemparte C. Saaby S. Bella M. Jørgensen KA. Angew. Chem. Int. Ed.  2005,  44:  2896 
• 4t Song J. Wang Y. Deng L. J. Am. Chem. Soc.  2006,  128:  6048 
• 4u Tillman AL. Ye J. Dixon DJ. Chem. Commun.  2006,  1191 
• 4v Zhang H. Mifsud M. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  9630 
• 4w Ramasastry SSV. Zhang H. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2007,  129:  288 
• 5 Rueping M. Azap C. Angew. Chem. Int. Ed.  2006,  45:  7832 ; Angew. Chem. 2006, 118, 7996
• 6a Rueping M. Azap C. Sugiono E. Theissmann T. Synlett  2005,  2367 
• 6b Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett.  2005,  7:  3781 
• 6c Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  6751 ; Angew. Chem. 2006, 118, 6903
• 6d Rueping M. Theissmann T. Antonchick AP. Synlett  2006,  1071 
• 6e Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  3683 ; Angew. Chem. 2006, 118, 3765
• 7a Rueping M. Sugiono E. Azap C. Angew. Chem. Int. Ed.  2006,  45:  2617 ; Angew. Chem. 2006, 118, 2679
• 7b Rueping M. Sugiono E. Moreth SA. Adv. Synth. Catal.  2007,  349:  759 
• 8 Rueping M. Sugiono E. Theissmann T. Kuenkel A. Köckritz A. Pews-Davtyan A. Nemati N. Beller M. Org. Lett.  2007,  9:  1065 
• 9 Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 ; Angew. Chem. 2007, 119, 2143
• For reviews, see:
• 10a Schreiner PR. Chem. Soc. Rev.  2003,  32:  289 
• 10b Pihko PM. Angew. Chem. Int. Ed.  2004,  43:  2062 ; Angew. Chem. 2004, 116, 2110
• 10c Bolm C. Rantanen T. Schiffers I. Zani L. Angew. Chem. Int. Ed.  2005,  44:  1758 ; Angew. Chem. 2005, 117, 1788
• 10d Yamamoto H. Futatsugi K. Angew. Chem. Int. Ed.  2005,  44:  1924 ; Angew. Chem. 2005, 117, 1958
• 10e Taylor MS. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  1520 ; Angew. Chem. 2006, 118, 1550
• 10f Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
• 11a Akiyama T. Itoh J. Yokota K. Fuchibe K. Angew. Chem. Int. Ed.  2004,  43:  1566 ; Angew. Chem. 2004, 116, 1592
• 11b Uraguchi D. Terada M. J. Am. Chem. Soc.  2004,  126:  5356 
• 11c Uraguchi D. Sorimachi K. Terada M. J. Am. Chem. Soc.  2004,  126:  11804 
• 11d Akiyama T. Morita H. Itoh J. Fuchibe K. Org. Lett.  2005,  7:  2583 
• 11e Akiyama T. Saitoh Y. Morita H. Fuchibe K. Adv. Synth. Catal.  2005,  347:  1523 
• 11f Rowland GB. Zhang H. Rowland EB. Chennamadhavuni S. Wang Y. Antilla JC. J. Am. Chem. Soc.  2005,  127:  15696 
• 11g Terada M. Sorimachi K. Uraguchi D. Synlett  2006,  133 
• 11h Hoffmann S. Seayad AM. List B. Angew. Chem. Int. Ed.  2005,  44:  7424 ; Angew. Chem. 2005, 117, 7590
• 11i Akiyama T. Tamura Y. Itoh J. Morita H. Fuchibe K. Synlett  2006,  141 
• 11j Storer RI. Carrera DE. Ni Y. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  84 
• 11k Seayad J. Seayad AM. List B. J. Am. Chem. Soc.  2006,  128:  1086 
• 11l Terada M. Machioka K. Sorimachi K. Angew. Chem. Int. Ed.  2006,  45:  2254 ; Angew. Chem. 2006, 118, 2312
• 11m Mayer S. List B. Angew. Chem. Int. Ed.  2006,  45:  4193 ; Angew. Chem. 2006, 118, 4299
• 11n Itoh J. Fuchibe K. Akiyama T. Angew. Chem. Int. Ed.  2006,  45:  4796 ; Angew. Chem. 2006, 118, 4914
• 11o Nakashima D. Yamamoto H. J. Am. Chem. Soc.  2006,  128:  9626 
• 11p Hasegawa A. Naganawa Y. Fushimi M. Ishihara K. Yamamoto H. Org. Lett.  2006,  8:  3175 
• 11q Chen X.-H. Xu X.-Y. Liu H. Cun L.-F. Gong L.-Z. J. Am. Chem. Soc.  2006,  128:  14802 
• 11r Kang Q. Zhao Z.-A. You S.-L. J. Am. Chem. Soc.  2007,  129:  1484 
• 15 For a review on the concept of combined acids, see: Yamamoto H. Futatsugi K. Angew. Chem. Int. Ed.  2005,  44:  1924 ; Angew. Chem. 2005, 117, 1958

12

Other achiral acids tested gave inferior results with regard to both reactivity and selectivity.

13

No reaction was observed with N-benzyl, N-phenyl, N-(4-methoxyphenyl), N-Boc, N-CBz, N-Bz, N-benzhydryl derivatives.

14

General Procedure for Direct Mannich Reaction
In a typical experiment acetophenone 3 (2 equiv), aldimine 2, catalyst 1c (10 mol%) and AcOH (20 mol%) were suspended in Bu₂O in a screw-capped vial and the resulting mixture was allowed to stir at r.t. for 60 h. Purification of the crude product by column chromatography on silica gel afforded the corresponding product 4.
3-(4-Chlorophenylamino)-1,3-diphenylpropan-1-one (4a) The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 43% yield and 86% ee. The ee was determined by HPLC using Chiralcel OD-H column [n-hexane-i-PrOH (90:10), flow rate 0.6 mL/min; major enantiomer: t _R = 25.3 min; minor enantiomer: t _R = 28.2 min); mp 162 °C; [α]_D +31.0 (c 1.0, CH₂Cl₂). IR (KBR): 3373, 2924, 1666, 1507, 1489, 1286, 1003, 820, 703 cm^-1. ESI-HRMS: m/z calcd for C₂₁H₁₈NOClNa [M + Na]⁺: 358.0975; found: 358.0974. ¹H NMR (250 MHz, CDCl₃): δ = 3.25-3.49 (m, 2 H), 4.55 (br s, 1 H), 4.80-4.94 (m, 1 H), 6.34-6.45 (m, 2 H), 6.90-6.99 (m, 2 H), 7.11-7.29 (m, 4 H), 7.30-7.42 (m, 3 H), 7.43-7.54 (m, 1 H), 7.78-7.87 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 46.1, 54.9, 114.9, 122.4, 126.2, 128.1, 128.7, 128.8, 128.9, 133.4, 136.6, 142.4, 145.5, 198.1.
3-(4-Chlorophenylamino)-1-phenyl-3- p -tolylpropan-1-one (4b)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 40% yield and 63% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 0.6 mL/min; major enantiomer: t _R = 18.8 min; minor enantiomer: t _R = 20.1 min]; mp 149-152 °C; [α]_D +21.4 (c 1.0, CH₂Cl₂). IR (KBr): 3449, 2843, 1595, 1492, 1250, 1095, 909, 776, 758, 536 cm^-1. ESI-HRMS: m/z calcd for C₂₂H₂₀NOClNa [M + Na]⁺: 372.1131; found: 372.1137. ¹H NMR (250 MHz, CDCl₃): δ = 2.23 (s, 3 H), 3.20-3.50 (m, 2 H), 4.50 (br s, 1 H), 4.76-4.91 (m, 1 H), 6.30-6.50 (m, 2 H), 6.89-6.98 (m, 2 H), 7.00-7.10 (m, 2 H), 7.15-7.26 (m, 2 H), 7.30-7.41 (m, 2 H), 7.42-7.54 (m, 1 H), 7.75-7.91 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 21.1, 46.3, 54.6, 114.9, 122.3, 126.2, 128.2, 128.7, 128.9, 129.6, 133.5, 136.6, 137.1, 139.4, 145.6, 198.2.
3-(4-Chlorophenylamino)-3-(4-chlorophenyl)-1-phenyl Propan-1-one (4c)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 53% yield and 64% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 0.6 mL/min; major enantiomer: t _R = 21.7 min; minor enantiomer: t _R = 24.4 min]; mp 140 °C; [α]_D +22.8 (c 1.0, CH₂Cl₂). IR (KBr): 3386, 1671, 1597, 1508, 1289, 1095, 1015, 810, 684 cm^-1. ESI-HRMS: m/z calcd for C₂₁H₁₇NOCl₂Na [M + Na]⁺: 392.0585; found: 392.0590. ¹H NMR (250 MHz, CDCl₃): δ = 3.19-3.48 (m, 2 H), 4.55 (br s, 1 H), 4.84 (t, J = 6.5, 12.5 Hz, 1 H), 6.26-6.44 (m, 2 H), 6.82-7.04 (m, 2 H), 7.14-7.31 (m, 4 H), 7.32-7.41 (m, 2 H), 7.44-7.54 (m, 1 H), 7.73-7.90 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 46.0, 54.3, 115.0, 122.7, 127.7, 128.1, 128.8, 129.0, 129.0, 133.1, 133.7, 136.5, 141.0, 145.3, 197.8.
3-(4-Chlorophenylamino)-3-(2-fluorophenyl)-1-phenyl Propan-1-one (4d)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 51% yield and 65% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 0.6 mL/min; major enantiomer: t _R = 38.3 min; minor enantiomer: t _R = 35.9 min]; mp 125-130 °C; [α]_D +20.2 (c 1.0, CH₂Cl₂). IR (KBr): 3368, 2924, 1666, 1597, 1488, 1286, 1220, 819, 757 cm^-1. ESI-HRMS: m/z calcd for C₂₁H₁₇NOClFNa [M + Na]⁺: 376.0880; found: 376.0872. ¹H NMR (250 MHz, CDCl₃): δ = 3.24-3.58 (m, 2 H), 4.66 (d, J = 4.5 Hz, 1 H), 5.04-5.21 (m, 1 H), 6.33-6.46 (m, 2 H), 6.89-7.04 (m, 4 H), 7.08-7.20 (m, 1 H), 7.28-7.41 (m, 3 H), 7.42-7.54 (m, 1 H), 7.80-7.90 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 44.2, 49.6, 114.8, 115.5, 115.8, 122.6, 124.5, 124.5, 128.2, 128.3, 128.4, 128.7, 128.8, 128.9, 129.0, 129.1, 133.6, 136.4, 145.2, 158.5, 162.4, 198.1.
3-(4-Chlorophenylamino)-1-phenyl-3- o -tolylpropan-1-one (4e)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 41% yield and 65% ee. The ee was determined by HPLC using Chiralcel OD-H column [n-hexane-i-PrOH (98:2), flow rate 0.6 mL/min; major enantiomer: t _R = 42.2 min; minor enantiomer: t _R = 55.4 min]; mp 149-153 °C; [α]_D +26.8 (c 1.0, CH₂Cl₂). IR (KBr): 3392, 2915, 1671, 1596, 1500, 1445, 1314, 1289, 1175, 1078, 818 cm^-1. ESI-HRMS: m/z calcd for C₂₂H₂₀NOClNa [M + Na]⁺: 372.1131; found: 372.1139. ¹H NMR (250 MHz, CDCl₃): δ = 2.25 (s, 3 H), 3.22-3.48 (m, 2 H), 4.49 (br s, 1 H), 4.82 (t, J = 6.8, 12.5 Hz, 1 H), 6.34-6.46 (m, 2 H), 6.90-7.02 (m, 2 H), 7.08-7.16 (m, 3 H), 7.30-7.54 (m, 3 H), 7.78-7.88 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 21.5, 46.3, 54.9, 114.9, 122.3, 123.3, 126.9, 128.2, 128.3, 128.7, 128.8, 128.9, 133.5, 136.6, 138.5, 142.5, 145.7, 198.2.
3-(4-Chlorophenylamino)-3-(2,5-dimethoxyphenyl)-1-phenylpropan-1-one (4f)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a colorless solid in 45% yield and 65% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 0.6 mL/min; major enantiomer: t _R = 23.6 min; minor enantiomer: t _R = 22.6 min]; mp 144-145 °C; [α]_D +19.6 (c 1.0, CH₂Cl₂). IR (KBr): 3413, 2929, 1684, 1599, 1496, 1280, 1221, 1092, 1045, 817 cm^-1. ESI-HRMS: m/z calcd for C₂₃H₂₂NO₃ClNa [M + Na]⁺: 418.1186; found: 418.1176. ¹H NMR (250 MHz, CDCl₃): δ = 3.03-3.21 (m, 1 H), 3.45-3.65 (m, 4 H), 3.83 (s, 3 H), 4.66 (br s, 1 H), 4.98-5.20 (m, 1 H), 6.27-6.42 (m, 2 H), 6.64 (dd, J = 3.3, 8.8 Hz, 1 H), 6.76 (d, J = 8.8 Hz, 1 H), 6.83-6.97 (m, 3 H), 7.30-7.53 (m, 3 H), 7.85-7.96 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 44.3, 50.8, 55.6, 55.8, 111.4, 112.3, 113.8, 114.8, 116.2, 122.1, 128.4, 128.6, 128.8, 129.1, 130.9, 133.3, 136.6, 145.6, 150.6, 153.9, 198.8.
3-(4-Chlorophenylamino)-1-phenyl-3-(thiophen-2-yl)-propan-1-one (4g)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as a yellowish solid in 39% yield and 65% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 1.0 mL/min; major enantiomer: t _R = 15.5; minor enantiomer: t _R = 14.2]; mp 126-130 °C; [α]_D +10.9 (c 1.0, CH₂Cl₂). IR (KBr): 3399, 2925, 1667, 1598, 1503, 1286, 1217, 1088, 1001, 813 cm^-1. ESI-HRMS: m/z calcd for C₁₉H₁₆NOClSNa [M + Na]⁺: 364.0539; found: 364.0529. ¹H NMR (250 MHz, CDCl₃): δ = 3.50 (d, J = 5.0 Hz, 2 H), 4.49 (br s, 1 H), 5.15-5.30 (m, 1 H), 6.44-6.60 (m, 2 H), 6.81-6.87 (m, 1 H), 6.89-6.94 (m, 1 H), 6.96-7.05 (m, 2 H), 7.10 (m, 1 H), 7.34-7.44 (m, 2 H), 7.46-7.55 (m, 1 H), 7.77-7.92 (m, 2 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 45.9, 50.9, 115.2, 123.1, 124.0, 124.3, 126.9, 128.1, 128.7, 129.0, 133.5, 136.7, 145.2, 147.2, 197.6.
3-(4-Chlorophenylamino)-3-(4,6-dihydropyren-3-yl)-1-phenylpropan-1-one (4h)
The title compound was isolated by column chromatography (n-hexane-EtOAc, 10:1) as an orange-colored solid in 22% yield and 56% ee. The ee was determined by HPLC using Chiralpak AD-H column [n-hexane-i-PrOH (80:20), flow rate 0.6 mL/min; major enantiomer: t _R = 23.2 min; minor enantiomer: t _R = 28.2 min]; mp 65-69 °C; [α]_D +122.3 (c 1.0, CH₂Cl₂). IR (KBr): 3397, 2923, 1681, 1598, 1496, 1314, 1260, 1088, 848 cm^-1. ESI-HRMS: m/z calcd for C₃₁H₂₂NOClNa [M + Na]⁺: 482.1288; found: 482.1273. ¹H NMR (250 MHz, CDCl₃): δ = 3.41-3.72 (m, 2 H), 4.82 (br s, 1 H), 5.88-6.06 (m, 1 H), 6.30-6.50 (m, 2 H), 6.78-6.96 (m, 2 H), 7.26-7.38 (m, 2 H), 7.40-7.52 (m, 1 H), 7.76-7.86 (m, 2 H), 7.88-8.07 (m, 4 H), 8.08-8.20 (m, 4 H), 8.39 (d, J = 9.3 Hz, 1 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 45.7, 51.2, 115.0, 121.4, 122.5, 123.4, 125.0, 125.2, 125.4, 125.5, 126.1, 127.3, 127.5, 127.5, 128.2, 128.4, 128.7, 128.9, 130.6, 131.4, 133.6, 135.4, 136.6, 145.6, 198.1.