寄稿論文カチオン性10族金属錯体を用いた不斉触媒反応の新展開：パラジウムエノラートを鍵とする反応を中心にして | 東京化成工業

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1 Si Sn B Al Ti Cu La Zn Ca 4 Li Mg B Al Ti Zr M M = Si, Sn LA X ' LA = chiral Lewis acid X ' M X ' M = metals (La, Zn) with chiral ligands or chiral ammonium ions M' M' = late transition metals Mild reactivity? Scheme. epresentative approaches to achieve enantioselective reactions with enolates. Ito-Saegusa d β d d d β d d

2 Ito-Saegusa reaction 3 Si d(ac) d(ii) β- elimination d- ur initial hypothesis: ucleophilc reactions should also occur. d(ii)l X 3 Si L-d(II) d(ii)l d(ii)l ' X ' ucleophilic reaction Scheme. ur original hypothesis. igure -6 Scheme 3 BIA μ i t 3-6 Tf d d d M Tf X - X - 3: M = d X = Tf or B 4 4: M = t Y i Y : Y = Tf 6: Y = Cl a-c Ar Ar d-f Ar Ar a: Ar = h: ()-BIA b: Ar = 4-C 6 4 : ()-Tol-BIA c: Ar = 3,- C 6 3 : ()-DM-BIA d: Ar = h: ()-SEGS e: Ar = 3,- C 6 3 : ()-DM-SEGS f: Ar = 3,-(t-Bu) -4-C 6 : ()-DTBM-SEGS igure. Chiral group 0 metal complexes used in our work. 3

3 Cl d Cl 7a AgX ( equiv) ( equiv) Acetone d X - aq. a ( equiv) C Cl d d X - Cl M Cl AgTf ( equiv) C Cl Tf M Tf M = i, d, t 3- Scheme 3. reparation of chiral metal complexes. 8 9 DM TMU Scheme 4 d d (I) β BIA d X d d 3 Si a ( mol%) h TMU, 0 C h up to 89% ee d Si 3 X - h 3 Si X X - d h d enolate (I) X - d h Scheme 4. Catalytic asymmetric aldol reaction via chiral d enolates. d d d μ Scheme d- d 4

4 3 Si M b ( mol%) M h C i-r DM, C h C i-r 8 M = 4--C 6 4 9%, 90% ee d X - X - Si 3 d h 3 Si h d enolate (I) X - M d h C i-r Scheme. Catalytic asymmetric Mannich-type reaction via chiral d enolates. d Scheme 6 d Brønsted d- μ Brønsted Lewis acid Brønsted acid Brønsted base d d - d d d X - X - X - X - Scheme 6. Chiral d complexes as acid-base catalysts. β β Scheme 7 d (II) d X - d d X -, X 3 d X - 3 Chiral palladium enolate (II) Scheme 7. ormation of chiral d enolates of,3-dicarbonyl compounds.

5 d (II) β Scheme 8 d cat. a or b (X = Tf) (-0 mol%) 3 3 T -0 ~ 0 C 3a-f 4 a-f t-bu t-bu t-bu t-bu Br 3a 93%, 93% ee 3b 9%, 90% ee 3c 88%, 89% ee 3d 88%, 90% ee 3e 8%, 94% ee Scheme 8. Catalytic asymmetric Michael reaction of β-ketoesters. d Scheme 9 μ b β 3a d Tf a b M Scheme 8 d d d b (X = Tf) Tf ( equiv) 0 C, h 3a t-bu ( equiv to d) T-d 8, rt, h b 4 ( equiv) d o reaction rt Tf - t-bu t-bu a 89%, 99% ee Cooperative action between d enolate and proton β-ketoester d d 3 Tf - Tf - t-bu d t-bu Scheme 9. Enantioselective Michael reaction of β-ketoesters. Y X 3 6

6 β 3 β β Scheme 0 mol a 7 8a T 9a T 9b d re 3a a (X = Tf) ( mol%) 89%, dr = 8 : 99% ee (major) 3 T, -0 C, 4 h C t-bu re face 6 7 3a a (X = Tf) ( mol%) d 0 C C t-bu 9 8a: = T; then 9a: 0%, 90% ee t-bu 8a: = 9a: 73%, 87% ee si face 8b: = T; then 9b: 90%, dr = 3.8 :, 99% ee (major) Scheme 0. Michael reactions using other acceptors. Scheme Scheme 9 β -Boc Table β β β 7

7 Table. Catalytic enantioselective Mannich-type reactions of β-ketoesters. d cat. a (X = Tf) C t-bu Boc (. mol%) Boc 3 T, M 3 C t-bu 3 0 entry ketoester imine ( 3 ) temp. time (h) yield dr ee a c a 3a 3a 3a 3a 3d 3d 3d 3d 3d 0a (C 6 ) 0b (p-c 6 4 ) 0c (o-c 6 4 ) 0e (o-clc 6 4 ) 0f (-furyl) 0a (C 6 ) 0b (p-c 6 4 ) 0c (o-c 6 4 ) 0e (o-clc 6 4 ) 0f (-furyl) 0 C 0 C 0 C 0 C 0 C rt rt rt rt rt : 90:0 93:7 9: >9: 86:4 90:0 96:4 :9 8:8 99/97 9/99 94/- b 93/- b 86/- b 98/9 97/8 98/- b 98/- b 96/99 a Major/Minor. b ot determined. c d was used. d Scheme mol d a β Scheme β d d 4a t 4c 4 Scheme 8

8 β-ketoester 3 d Tf - t-bu C t-bu n t-bu a ( mol%) T 3a,b -0 ~ 0 C, < 3 h n C t-bu Allyl h C t-bu 8%, dr = 6.3: 99% ee / 98% ee Et h C t-bu 8%, dr = : 99% ee / 9% ee Bn h C t-bu 7%, dr =.: 99% ee / 99% ee Allyl h C t-bu 70%, dr = 4.: >99% ee / 9% ee Et C t-bu 3%, dr = 3.4: >99% ee / >99% ee Scheme. Catalytic asymmetric aldol-type reaction with acetals. 3d Bn Bn t cat. 4c (0 mol%) Bn h C t-bu h T -0 C, 4 h 3 4 7%, dr = 4: 89% ee (major) ZnCl ab 4 74% DIBAL- 67% Bn h C t-bu Bn h C t-bu Scheme. Catalytic asymmetric aldol-type reaction with acetals using t complex.,, Scheme 3 d, (Boc) 6 Scheme 3 7 e μ e 9

9 G X - d ' ' ' C G C ' mol% e (X = Tf) C i-r (Boc) C i-r Boc 3 C Boc 3 3 Cl C Cl, 0 C 4 4 t-bu C i-r rt, 30 min. C i-r 6 7 a b c d 89%, 8% ee 98%, 8% ee 93%, 94% ee 9%, 97% ee (. h) (. h) ( mo% e, 3 h) ( h) Br e 7%, % ee ( h) f 94%, 8% ee ( mol% e, 6 h) g 93%, 96% ee (. h) h 97%, 90% ee (3 h) Scheme 3. Catalytic asymmetric Mannich-type reaction of malonate to dihydroisoquinolines., α DDQ Scheme 4 DDQ 3e 8 (Boc) 7c ee ipecac 3 0

10 C i-r mol% C i-r d cat. 3e (X = Tf) (. equiv) (Boc) Boc (. equiv) C Cl, 0 C C i-r C i-r 8 DDQ ( equiv) 7c slow addition over 0 h 97%, 86% ee 9 0 mol% 3e (X = Tf) malonate (. equiv) C Cl, rt DDQ ( equiv) slow addition over 0 h i-r C 30 74%, 86% ee C 3 99% ee Scheme 4. xidative Mannich-type reaction starting from tetrahydroisoquinolines. sp sp 3 α Table d Togni Ti-TADDL β Table d μ c f β 3 SI 3 β C-C μ T d [hmim][b 4 ] Table 3

11 Table. Catalytic asymmetric fluorination reactions of β-ketoesters. ' X - ' X acidic co-product S h. mol% d cat. C t-bu S h Et, M 8-7 h SI 3 3 (. eq) 33 C t-bu C t-bu n 3a: n = 3b: n = t-bu 3c 3d: = = C t-bu 3f: = h, = 3g: =, = Et 3h: = Et, = entry a b 7 8 ketoester 3a 3b 3c 3d 3f 3f 3g 3h product 33a 33b 33c 33d 33f 33f 33g 33h catalyst (X) f (Tf) c (B 4 ) c (Tf) f (Tf) c (B 4 ) c (Tf) c (Tf) c (Tf) temp. ( C) yield c ee a i-r was used. b g scale. mol% c. c Lower yield due to the volatility of 33d. Table 3. ecovery and reuse of d catalyst in ionic liquid. c in [hmim][b 4 ] [hmim][b 4 ] 3f and 3 recycle rt 60 h - B 4 Et extraction 33f and (hs ) in Et cycle yield 3 4 a 84 h ee cycle yield a ee β 3 37 β Scheme

12 h. TA. C (7%) C 33f: = t-bu 34: = h Si TBA (83%) Et 3 Si TA (9%) C h 3 C h 37. h 3, DEAD, DA (79%). d/c,, (Boc) (80%). h 3, DEAD, DA (9%). d/c,, (Boc) (78%) Boc C h 36 Boc C h 38 Scheme. Conversion of the fluorinated β-ketoester. tert 39 4 Scheme 6 4 μ f ee 4 d 4 43 Bn C t-bu n n =, C t-bu. mol% f (X = Tf) 3 (. equiv) i-r, rt, 4 h ~98% ee. mol% f (X = Tf) 3 (. equiv) Et, rt, 48 h Bn C t-bu n C t-bu d Tf - t-bu base B 3 -T Bn 4,6-lutidine (0. equiv) %, 98% ee Scheme 6. eactions of other related compounds. β 44 Table 4 β d 4 TMSI 3

13 Table 4. luorination reactions of β-ketophosphonates ' -0 mol% (Et) 3 (X = Tf) (Et) (. equiv) Et, M, rt h 4 (Et) (Et) (Et) 44e n n 44a: n = 44c: n = (Et) 44b: n = 44d: n = h 44f entry substarte 39a 39b 39c 39d 39d 39d 39e 39f catalyst (mol %) c () c () c () c () c () c () e (0) e (0) yield ee Scheme 7 BMS 46 d Boc 47 Cl 3 C BMS-043 (Maxiost TM ) (46) [hase III trial for stroke] low yield low ee t-bu 47 t-bu d X - Scheme 7. Catalytic asymmetric fluorination reactions of oxindoles. μ c i-r Table d re 4

14 Table. Catalytic asymmetric fluorination reactions of -Boc oxindoles. Boc 47 (racemate) h (47a) p-c 6 4 (47b) p-c 6 4 (47c) (47d) 3 (. equiv) yield ee mol% (S)-c (X = Tf) i-r, 0 C - rt -8 h Et (47e) C C()C 3 (47f) Bn (47g) i-bu (47h) Boc 48 yield ee SI Tf - d t-bu utative d enolate. BMS 46 Scheme 8 47a 49 0 Boc BMS -Boc i Shibata Toru Cl. mol% (S)-c Cl Cl 3 (. equiv) ) TA, 7% 3 C acetone ) recrystallization 0 C, 8 h 3 C 7% 3 C Boc Boc 90%, 7% ee 49 (racemate) 0 (S)-BMS-043 (46) >99% ee Scheme 8. Application to asymmetric synthesis of the BMS compound. d Scheme 9 T 4. mol% (S)-c (X = Tf) 3 (. equiv) T, rt, 43 h Boc Boc Boc 3 9%, % ee 9% C -DCE ( : ) Boc rt, 8 h Boc 4 3%, 93% ee Scheme 9. Catalytic asymmetric monofluorination-solvolysis of oxindole.

15 α Scheme 6 d SI Scheme 0 i a ee Scheme 0 i a d 3a a 6a ee 6a L L M LA h S a Base 3 LA h LA L L M S S h Sh h 6a S M: Bidentate Lewis acid LA: Monodentate Lewis acid a 3 (. equiv) 0 mol% i cat. 3 SiTf (. equiv),6-lutidine (. equiv) C Cl, 4 h h S 6a i cat. temp. yield ee a rt 99 8 a -0 C a -0 C mol% 6a Et 3 SiTf,6-lutidine (. equiv) Toluene, -0 C, 4 h 6a TESTf yield ee. equiv equiv Scheme 0. A novel trinary system for asymmetric fluorination of a. Table 6 ee Scheme 9 6 6

16 Table 6. Catalytic asymmetric monofluorination of aryl acetic acid derivatives. X i cat. 6a SI (. equiv) Et 3 SiTf toluene, -0 C, 0 min.,6-lutidine (. equiv) -0 C, 4 h X 6 entry substrate X catalyst (mol %) yield ee a b c d e f g h S S S S S S S h p-c 6 4 p-c 6 4 m-c 6 4 o-c 6 4 -naphthyl -naphthyl h Scheme 6a 6a Weireb 7 h S 6a (99% ee after enrichment) () Cl (3 equiv) 3 Al (3 equiv) C Cl, 0 C, 3 h 88% Li, T- 0 C, h quant. h 7 (99% ee) 3 SiC h h, rt 83% 8 9 (99% ee) Scheme. Conversion of the fluorinated product. α β β d μ ' Table 7 7

17 6a mol ee 6a Table 7 entry 6 mol Table 7. Catalytic asymmetric conjugate addition of amines. a ' Tf L d Tf - L' ' L, L' =, T ' entry 3 a b 8 b a (X = Tf) ' ' Tf T, M (. equiv) 0-40 C Et BnC BnC ' p-c 6 4 (a) C 6 (b) p-c 3 C 6 4 (c) p-c 6 4 (a) p-c 6 4 (a) p-c 6 4 (a) Bn (d) Bn (d) cat. (mol %) 0. time (h) yield ee a T/toluene = /. b The product was isolated as the corrsponding methyl ester. 60 Scheme a 6c α d α 66 ee Et 63 p-c 3 C 6 4 Tf 6c (. equiv) 0 mol% a (X = Tf) 3 C Toluene, 40 C, 4 h p-c 3 C 6 4 (0. equiv) Et 64 98%, 89% ee known 3 C Et C 3 Et torcetrapib (CET inhibitor) C 3 6 Bn p-c 6 4 Tf 6a (. equiv) mol% a (X = Tf) T, rt, 8 h 66 80%, 94% ee Scheme. Catalytic asymmetric reactions using carbamate-type substrates. Bn 8

18 μ d β d Scheme 3 β β 67 a 68 ee d C 3 CD β 69 MS Et β- elimination a d X - C 3 C d X -. mol% a (X = Tf) h Et, rt h time (h) Et (67a) 3 i-r (67b) c-ex (67c) 0. C 3 (67d) yield ee i-r. mol% a (X = Tf) i-r D h C 3 CD, rt, 6 h h 67b 69 99%, 86% ee Scheme 3. Catalytic asymmetric conjugate reduction of enones. 70 Scheme 4 7 (S)- BIA μ a 7 ee mol 7 (S) C (S)-a (X = Tf) C a yield ee Et, rt h 7 7 h. mol% 0. mol% BBr 3. recryst. C h 79%, >99% ee h Warfarin (anti-coagulant) (70) Scheme 4. Catalytic asymmetric synthesis of (S)-warfarin. 9

19 d μ d d ì. Comprehensive rganic Synthesis; Trost, B. M., leming, I., eathcock, C.., Eds.; ergamon: ew York, 9, Vol... Modern Aldol eactions, Vol., ;. Mahrwald, Ed.; Wiley-VC: Weinheim, Ito, Y.; irano, T.; Saegusa, T. J. rg. Chem. 978, 43, a) okami, J.; Mandai, T.; Watanabe,.; hyama,.; Tsuji, J. J. Am. Chem. Soc. 989,, 46. b) okami, J.; Watanabe,.; Kawada, M.; hyama,.; Tsuji, Tetrahedron Lett. 989, 30, a) Sodeoka, M.; amashima, Y. Bull. Chem. Soc. Jpn. 00, 78, 94. b) Sodeoka, M.; amashima, Y.; ure Appl. Chem. 006, 78, 477. c) amashima, Y. Chem. harm. Bull. 006, 4, 3. d) Sodeoka, M.; amashima, Y.; ure Appl. Chem. 008, 80, ujii, A.; agiwara, E.; Sodeoka, M. J. Am. Chem. Soc. 999,, a) Sodeoka, M.; hrai, K.; Shibasaki, M. J. rg. Chem. 99, 60, 648. b) Sodeoka, M.; Shibasaki, M. ure Appl. Chem. 998, 70, Kobayashi, S.; Ueno, M. In Comprehensive Asymmetric Catalysis; Jacobsen, E.., faltz, A., Yamamoto,., Eds.; Springer: Berlin, 004; Supplement, Chapter a) agiwara, E.; ujii, A.; Sodeoka, M. J. Am. Chem. Soc. 998, 0, 474. b) ujii, A.; agiwara, E.; Sodeoka, M. J. Synth. rg. Chem. Jpn. 000, 8, amashima, Y., Sodeoka, M., In andbook of C- Transformation; Dyker. G., Ed.; Wiley-VC: Weinheim, 00; Vol., p amashima, Y.; otta, D.; Sodeoka, M. J. Am. Chem. Soc. 00, 4, 40.. amashima, Y.; otta, D.; Umebayashi,.; Tsuchiya, Y.; Suzuki, T.; Sodeoka, M. Adv. Synth. Catal. 00, 347, amashima, Y.; Sasamoto,.; otta, D.; Somei,.; Umebayashi,.; Sodeoka, M. Angew. Chem. Int. Ed. 00, 44,. 4. amashima, Y.; Sasamoto,.; Umebayashi,.; Sodeoka, M. Chem. Asian J. 008, DI: 0.00/asia Lou, S.; Dai,.; Schaus, S. E. J. rg. Chem. 007, 7, 9998, and references therein. 6. or enantioselective hydroxymethyaltion of β-ketoesters: ukuchi, I.; amashima, Y.; Sodeoka, M. Adv. Synth. Catal. 007, 349, Umebayashi,.; amashima, Y.; ashizume, D.; Sodeoka, M. Angew. Chem. Int. Ed. 008, 47, Sasamoto,.; Dubs, C.; amashima, Y.; Sodeoka, M. J. Am. Chem. Soc. 006, 8, Dubs, C.; amashima, Y.; Sasamoto,.; Seidel, T. M.; Suzuki, S.; ashizume, D.; Sodeoka, M. J. rg. Chem. 008, 73, 89. 0

20 0. a) Kirsch,. Modern luoroorganic Chemistry: Synthesis, eactivity, Applications; Wiley-VC: Weinheim, 004. b) iyama, T., Kanie, K., Kusumoto, T., Morizawa, Y., Shimizu, M. rganofluorine Compounds: Chemistry and Applications; Springer: Berlin, 000. c) Müller, K.; aeh, C.; Diederich,. Science, 007, 37, 88.. intermann, L.; Togni, A. Angew. Chem. Int. Ed. 000, 39, a) amashima, Y.; Sodeoka, M. Synlett 006, 467. b) amashima, Y.; Sodeoka, M. J. Synth. rg. Chem. Jpn. 007, 6, 099, and references therein. 3. amashima, Y.; Yagi, K.; Takano,.; Tamás, L.; Sodeoka, M. J. Am. Chem. Soc. 00, 4, amashima, Y.; Takano,.; otta, D.; Sodeoka, M. rg. Lett. 003,, 3.. Suzuki, T.; Goto, T.; amashima, Y.; Sodeoka, M. J. rg. Chem. 007, 7, a) amashima, Y.; Suzuki, T.; Shimura, Y.; Shimizu, T.; Umebayashi,.; Sasamoto,.; Sodeoka, M. Tetrahedron Lett. 00, 46, 447. b) amashima, Y.; Suzuki, T.; Takano,.; Shimura, Y.; Tsuchiya, Y.; Moriya, K.; Goto, T.; Sodeoka, M. Tetrahedron 006, 6, or cyanophosphonates: Moriya, K.; amashima, Y.; Sodeoka, M. Synlett 007, ewawasam,.; Gribkoff, V. K.; endri, Y.; Dworetzky, S. I.; anwell,. A.; Martinez, E.; Boissard, C. G.; ost-munson, D. J.; Trojnacki, J. T.; Yeleswaram, K.; ajor, L. M.; Knipe, J.; Gao, Q.; errone,.; Starrett, Jr., J. E. Bioorg. d. Chem. Lett. 00,, amashima, Y.; Suzuki, T.; Takano,.; Shimura, Y.; Sodeoka, M. J. Am. Chem. Soc. 00, 7, Shibata,.; Kohno, J.; Takai, K.; Ishimaru, T.; akamura, S.; Toru, T.; Kanemasa, S. Angew. Chem. Int. Ed. 00, 44, Suzuki, T.; amashima, Y.; Sodeoka, M. Angew. Chem. Int. Ed. 007, 46, Davis,. A.; an, W. Tetrahedron Lett. 99, 33, Xu, L.-W.; Xia, C.-G. Eur. J. rg. Chem. 00, 633, and references therein. 34. amashima, Y.; Somei,.; Shimura, Y.; Tamura, T.; Sodeoka, M. rg. Lett. 004, 6, Guinó, M.; hua,..; Caille, J.-C.; ii, K. K. J. rg. Chem. 007, 7, 690, and references therein. 36. a) Mueller, J. A.; Goller, M. S.; Sigman, M. S. J. Am. Chem. Soc. 004, 6, 974. b) Konnick, M. M.; Gandhi, B. A.; Guzei, I. A.; Stahl, S. S. Angew. Chem. Int. Ed. 006, 4, a) Tsuchiya, Y.; amashima, Y.; Sodeoka, M. rg. Lett. 006, 8, 48. b) Monguchi, D.; Beemelmanns, C.; ashizume, D.; amashima, Y.; Sodeoka, M. J. rganomet. Chem. 008, 693, or representative examples: a) Moritani, Y.; Appella, D..; Jurkauskas, V.; Buchwald, S. L. J. Am. Chem. Soc. 000,, b) Lipshutz, B..; Servesko, J. M. Angew. Chem. Int. Ed. 003, 4, c) Kanazawa, Y.; Tsuchiya, Y.; Kobayashi, K.; Shiomi, T.; Itoh, J.; Kikuchi, Y.; Yamamoto, Y.; ishiyama,. Chem. Eur. J. 006,, or other asymmetric syntheses: alland,.; ansen, T.; Jørgensen, K. A. Angew. Chem. Int. Ed. 003, 4, 49, and references therein. (eceived Aug. 008) Yoshitaka amashima Mikiko Sodeoka arvard

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名称未設定 1 a C CF b c 4 5 Me Me S Jacobsen's catalyst Scheme 1. eagents and conditions: (a) C (1.5 equiv), Jacobsen's catalyst (0.05 equiv), toluene, 0 C, 40 h, then trifluoroacetic anhydride (4.0 equiv), 60 C,

寄稿論文 カチオン性10族金属錯体を用いた不斉触媒反応の新展開：パラジウムエノラートを鍵とする反応を中心にして | 東京化成工業

寄稿論文カチオン性10族金属錯体を用いた不斉触媒反応の新展開：パラジウムエノラートを鍵とする反応を中心にして | 東京化成工業