untitled

Transcription

1

2 H H [u(salen)(h)()] air, hν, rt * * * * H (1) 99%, 93% ee

3 n-c 9 H 19 + n-c 8 H 17 (1 : 1) H H ()u(salen), hν, air d 6 -benzene, rt, 12 h n-c 9 H 19 H quantitative n-c 8 H 17 (2) p-clc 6 H 4 Me S Ti(salen) (cis-β) urea H 2 2, MeH, 0 C p-clc 6 H 4 S + Me - 99% ee, 88% (3) racemate k rel ~ 2 L (88% ee) + AL (97% ee) fast-reacting isomer slow-reacting isomer urea þh 2 2 Zr-salen ( 1 : 24 ) di-µ-oxo Ti(salalen) 30% H 2 2 (1 eq), rt Ph ()u(salen) SES 3,0 C + ( 39 : 1 ) (5) >99% ee, 99%, T= 4,600 Ph 92% ee, 99% (4) L= normal lactone AL= abnormal lactone T= turnover number of catalyst * (6) SES= β-trimethylsilylethanesulfonyl SES Ph + CH Br 2 equiv,-dbfx/ph ZnBr 2 (10 mol%) + AgCl 4 MS 4A (500 mg/mmol) rt in CH 2 Cl 2 Ph Ph + BnH 2,-BX/o-HBn + Cu(Tf) 2 (10 mol% each) CH 2 Cl 2, -20 *C Ph Ph Ph Br CH (7) 99% ee, 96% endo- only HBn (8) 94% ee, 92%

4 * i-pr,-dbfx/ph i(cl 4 ) 2 i(cl 4 ) 2 (10 mol%) i-pr * (9) TMP (10 mol%) 2 CH 2 Me2 / THF = 1:1 v/v at -20 þc TMP= 2,2,6,6-tetramethylpiperidine 97% ee, 94% 1 SiMe 3 CuCl 1 C 2 Si Si Me 3 Si Cl Si = TBDMS Si = TBDMS 1 Me 1) LDBB 2) Zn II Li Cu 1) Li, cat. Fe III Si 2) E + Me 1) MgX, cat. Fe III Si 2) E + 1) cat. MnBr 2 / DEE 2) (CF 3 C) 2 Me 2 CCl (E) E (Z) Si 3) E 1 Me CCF 3 or E Me E 1 CCF 3 (1 ) H (12) Me Me Introduction of chirality and Cyclization H ' Me Me * L L Pd * Me Me H Pd L L C1-Substituted tetrahydroisoquinolines (13) L L = PPh 2 2-(Phosphinophenyl)pyridine

5

6

7 H M Y M Y trans M M hydroperoxo peroxo oxo metallosalen complex= --- = salen ligand Y M Y cis-β (Λ) Fig. 1 Y M Y M Y Y cis-β ( ) enantiomeric Y-Y = bidentate ligand Fig. 2 M cis-β ( ) HH = bidentate ligand

8 t-bu Cl Ti Cl Bu-t t-bu H 2, Et 3 Ti Bu-t Ti di-µ-oxo complex (1) HH Ti cis-β ( ) concave site () Cl Ti Cl Ph Ph () 2 H 2, Et 3 Ti HH Ti di-µ-oxo complex (3) Ti Scheme 1 Ph S Me cat. (2mol%), oxidant (1.0 eq) MeH Ph S+ * Me Scheme Ph S+ S + * Me Me * Cl 98% ee 99% ee Me - - S + Me * 1: 30%H 2 2, 10% ee 3: 30%H 2 2, 76% ee 3: UHP, 94% ee 3: UHP (0 C), 98% ee - S + * 96% ee 93% ee 93% ee * Me S + - Ph Me n-c 7 H 15 * Me S + - S S % ee Fig. 3 99% ee trans /cis =93 : 7 Ph - * S S + 99% ee

9 B: H H L s L s : L.. Criegee intermediate H :B s 45 3 > B: Scheme 3 H L L.. : s s Ph t-bu catalyst, H 2 2 CH 2 Cl 2, rt Ph Co + Co + Bu-t F SbF - 6 SbF - 6 Bu-t t-bu F F 4 5 4: 20%, 0% ee 5: 30%, 57% ee 5: 72%, 77% ee (EtH, -20 C) Scheme 4 F

10 6 (matching pair) + slow isomer normal lactone 40 : 1 ent-abnormal lactone (racemic) 6, UHP, ClC 6 H 5 r.t. + (mis-matching pair) fast isomer ent-normal lactone 1 : 35 abnormal lactone 6 (5 mol%), UHP CH 2 Cl 2, r.t. = lc 6 H 5 : 87% ee, 68% = p-mec 6 H 4 : 84% ee, 43% = n-c 8 H 17 : 81% ee, 63% 6 (5 mol%), UHP H H Y= Ph CH 2 Cl 2, r.t. 94% ee, 99% Y Zr Y Ph Ph Scheme 5 6

11 , 30% H 2 2 (1 eq) CH 2 Cl 2 or AcEt, T * * Y 1) Ti(Pr-i) 4 H H 2) H Y 2 (a,s)-salen ligand H Ti Ti H 7 (a,s)-salaren ligand --H- = Ph (S) H Ph () Ph nc 6 H 13 >99% ee, >99% 99% ee, 87% 88% ee, 64% 95% ee, 75% 93% ee, 90% 82% ee, 70% Scheme 6 H Ti Ti H 8 Fig. 4 Ti H Ph Ph 8, air, rt k H S /k = 20 H Ph 65% conversion >99.5% ee + u Cl Ph Ph Scheme 7 8

12 H H 9, hν, air d 6 -benzene, rt, 12 h quantitative H 0% H n H + Ph H 9, air, hν ether H cat, hν, air d 6 -benzene, rt, 12 h 9: k 1 : k 2 =15 : 1 10: k 1 : k 2 = >50 : 1 n H n= 1: 81% n= 2: 95% H Ph u X 9: = t-bu, X= Cl 10: = CH 3 (C 2 H 5 ) 2 C-, X= H Scheme H H H 12 (2 mol%) H hν, rt, air, benzene 80% ee, 67% H Ph Ph 11 (2 mol%) H air, hν, rt, CHCl Ph 3 Ph 81% ee, 82% u X Ar Ar a Ph Ph H H 13 (2 mol%) air, hν, rt, CHCl 3 Ph H 11: Ar= p-(c 6 H 6 )C 6 H 4, = Me, X= H 12: Ar= Ph, = Me, X= Cl 13: Ar= p-(tbdps)c 6 H 4, = H, X= Cl 14: Ar= Ph, = Me, X= H Ph 93% ee, 77% Scheme 9

13 Single Electron Transfer ' ' H ' ' 2 - : H : H. + H [u red ] hν [u III ] hν X [u IV ] [u III ] X X X : : : Hydrogen atom transfer : ' [u III ] X [ ] = salen ligand ' Scheme 10 Ligand exchange ' + H 2 2 H

14 catalytic cycle of oxidation of mono-ols 12 or 14 hν, H H u III L 2 SET H ' H u III L catalytic cycle of oxidation of diols 12 or 14 hν, H H 2 H H u III L hν 'C= Scheme 11 SET H 'CHH Ligand exchange hν H Scheme 12 H u III L Ligand exchange H H H H ' Intramolecular Hydrogen Atom transfer u III L H 2 2 Intermolecular Hydrogen Atom transfer u III L H 2 2

15 ü (Scheme 13) Ph Me S (C)u(salen) 15, Ts 3 MS, CH 2 Cl 2, rt S Ph 1) 15, Ts 3 MS, CH 2 Cl 2, rt 2) KH Ph * S + Me - Ts 98% ee, 99% HTs 86% ee Scheme 13 C u X Ph Ph 16 Ph * Ph Me S + Me Cl 3 CMe 2 CC 3 S - CCMe 2 CCl % ee, 93% Scheme a Ph Ts Ph Ts 3 Ph % ee, 71% T= C u Ph Ar HC 2 C(CH 3 ) 2 CCl 3 Scheme

16 C u Ar Ar 18: Ar= F F Cl 19: Ar= F F CH 3 20: Ar= TMS Fig. 5 Cl n-c 6 H 13 Ph 19t, p-ch 3 C 6 H 4 S 2 3 (1.0 eq.) MS 4A, CH 2 Cl 2, rt, 2, 24h 19, p-ch 3 C 6 H 4 S 2 3 (1.0 eq.) MS 4A, CH 2 Cl 2, rt, 2, 24h S 2 C 6 H 4 CH 3 -p 85% ee, T= 867 n-c 6 H 13 S 2 C 6 H 4 CH 3 -p 86% ee, T= 10 Ph cat, p- 2 C 6 H 4 S 2 3 (1 eq) MS 4A, CH 2 Cl 2, rt, 2, 24h Scheme Ph S 2 C 6 H 4 2 -p 15: 82% ee, T= 5 19: 84% ee, T= 34 20: 81% ee, T= , SES 3 (1 eq) MS 4A, CH 2 Cl 2, 2, 24 h SES Scheme 17 = Ph: 91% ee, T= 260 (rt) =p-brc 6 H 4 : 92% ee, T= 98 (0 C) =PhC C: >99% ee, T= 51 (0 C) indene: 98% ee, T= 13 (reflux) = n-c 6 H 13 : 77% ee, T= 6 (reflux)

17 H M X H M X M X M X Doyle's proposal possible transition states M Ar Ar 2' 15: M= ()ucl, = Ph 21: M= ()ucl, = Me 22: M= Co, = Me Fig (5 mol%), hν 2 H 3 CH 2 THF (5 ml), r.t., 16 h = Ph, 2, 3 =H: 94% ee, 78% 1 = (CH 3 ) 2 C=CH(CH 2 ) 2, 2 = Me, 3 =H: 90% ee, 70% (5 mol %) 2 H 3 CH 2 -methylimidazole THF, r.t. 1 = Ph, 2, 3 =H: 97% ee, 67% 1 1 = Ph, 2 = Me, 3 =H: 90% ee, 70% 3 Scheme 18

18 Ph 23, UHP AcEt, rt Ph UHP= urea H % ee, 62% 23, C 6 H 5 SH CH 2 Cl 2, rt, 24 h C 6 H 5 S 92% ee, 81% Y Hf Y Ph Ph Hf Y= Ph water 23 Scheme

19 Mukaiyama-aldol reaction Ph(CH 2 ) 3 CH + TMS 1) 24 (2.5 mol %) i-prh (1 eq.) 2,6-Cl 2 C 5 H 3 (1 eq.) toluene, -20 C 2) CF 3 CH Ph(CH 2 ) 3 H 97% ee, 87% Sakurai-Hosomi reaction Ph(CH 2 ) 3 CH + Sn n Bu 3 (1.1 eq) 25 (5 mol%) TBME/ CH 2 Cl 2, -20 ÞC, 3 days Ph(CH 2 ) 3 H 92% ee, 80% Ph Ph Cr + Ph Ph Cr + Ph Ph 2'' SbF 6-24 Scheme 2 26 SbF 6-25 Me 2 Zn, Ph, 26 (8 mol%) H Ph Toluene/CH 2 Cl 2, r.t., 2days * Ph Ph ) (S) H H Ph Ph = Me: 80% ee, 74% = Et: 81% ee, 49% = n-pr: 87% ee, 61% = n-bu: 86% ee, 34% 26 Scheme 21

20 27 27 H + P H Me Me 27 (10 mol%) THF, -15 C, 48 h H Me * P Me = Ph: 90% ee, 87% = p-( 2 )C 6 H 4 : 94% ee, 95% = PhCH 2 CH 2 : 91% ee, 94% = (CH 3 ) 2 CH: 89% ee, 89% t-bu Al Cl Bu-t Bu-t 27 t-bu Scheme 22

21 Me Me H + P H Me Me H 27 (10 mol%) Me * P THF, -15 C, 48 h Me = Ph: 87% ee, 85% = p-brc 6 H 4 : 95% ee, 100% (-protecting group= CH(C 6 H 5 ) 2 Scheme 23 = p-(ch 3 )C 6 H 4 : 90% ee, 92% = CH 3 (CH 2 ) 7 : 89% ee, 79%)

22 CH Ph + Ph Br 2 equiv ZnBr 2,-DBFX/Ph ZnX 2 (10 mol%) + nagcl 4 MS 4A (500 mg/mmol) rt in CH 2 Cl 2 n (equiv) Uncatalyzed Time/h Yield/% Ph endo:exo 49:51 81:19 95:5 88:12 Ph Br CH and exo-isomer % ee -/- 16/3 94/51 97/94 ( )

23 (eq. 4) (eq. 5)

24 (eq. 6)

25

26 Double Catalytic Activation Electrophile Y MtlLn* LA catalyst Amine + MtlLn* Amine MtlLn* X C Michael addition C Amine Y C C Base catalyst * C Up to 94% ee ucleophile H C X (eq. 3) (eq. 4) 2 CH 2,-DBFX/Ph i(cl 4 ) 2 3H 2 (10 mol%), TMP (10 mol%) in Me 2 /THF = 1:1 v/v at -20 C X Time/h Yield/% % ee Me Me Me Et n-pr i-pr c-c 6 H 11 t-bu H Br I H H H H H 2 equiv + Me Me Et n-pr i-pr c-c 6 H 11 1-Propenyl 2-Furyl C 2 Me Ph X X ,-DBFX/Ph i(cl 4 ) 2 3H 2 (10 mol%), TMP (10 mol%), Ac 2 (2 equiv), THF (0.1 M), rt Br I Br Br Br Br Br Br Br Br Time/h Yield/% a Determined by chiral HPLC, b nd: not determined nd b ee/% a (eq. 5)

27 a CH 2 2 a DBFX/Ph + i(ac) 2 4H 2 (10 mol%), Additive, Me 2 / Solvent = 1 / 1, rt ( ) Solvent THF THF THF Additive mol% Time/h none TMP MS 4A - 10 b Yield/% %ee quant > t-buh t-buh t-buh t-buh t-buh t-buh none TMP CH 3 CH CF 3 CH MS 4A MS 5A b 500 mg/mmol b b quant 46 - quant quant 98 >99 >99 - >99 >99

28 1 SiMe 3 CuCl 1 C 2 Me 3 Si Cl Cu 2 CCl α γ 1

29 E Me 1) Li, cat. Fe III Si Si 2) E + (E) Si = TBDMS Me E 1) MgX, cat. Fe III Si (Z) 2) E + Me Si Si = TBDMS Me 1) LDBB 2) Zn II Si 3) E 1 Me E 1 H ) cat. MnBr 2 / DEE CCF 3 CCF 3 Li 2) (CF 3 C) 2 or,,-(dmf) Michael

30

31 * L M L Square planar or tetrahedral metal complex bearing bidentate ligand H 2 2 Criegee adduct complex 1 1 H H H H 1-Pd(SbF 6 ) 2 (5 mol %) UHP THF, -60 C = Ph: 91%, 80% ee = 2-aphthyl: 94%, 83% ee 1-Pd(SbF 6 ) 2 (5 mol %) UHP THF, -40 C H H * L L H M H PPh 2 H 89%, >99% ee 2-(Phosphinophenyl)pyridine (1) *

32 * 1 Me Me Introduction of chirality and Cyclization H ' Me Me * L L Pd * Me Me H Pd L L C1-Substituted tetrahydroisoquinolines 2 Me Me 1) LAH 2) ClC()Et, pyridine 3) K 2 s 4 2H 2 0 4) abh 4 66% Me HCCF 3 Pd 2 (dba) 3 CHCl 3 Me (1.5 mol%) Me CCF3 Piv 1 (3.0 mol%) 2 K 2 C 3 3 CH 2 Cl 2, rt 89%, 88% ee Me Me 4a: = H 4b: = C()C 6 H 3 (3,5-2 ) CEt 90% 94% 1) p-tscl, DMAP 2) LAH 61% Me Me ()-(+)-Carnegine (5) 1 3 4b 55 C() L * L Pd L * Pd L Y X X L * Pd L C() X L Y * Pd L C Introduction of chirality and Cyclization Y Y X C *

33 1 1 C() 1 (5 mol%) [Pd(C 3 H 5 )Cl] 2 (2.5 mol%) Y X X= Y= ; 71% ee X= Bn, Y= ; 86% ee or Y X X= Bn, Y= ; 81% ee X= Y= Bn; 86% ee C() nucleophile, base 1 (a) ca. 3.5Å (b) 7 C7 PPh 2 Pd Cl Cl Cl1 PdCl 2-1 Pd Cl2 P C7 Cl1 Structure of PdCl 2-1 complex (hydrogen atoms are omitted for clarify). (a) Front view from chloro ligand; (b) top view from isopropyl group. Pd 2.392Å P 2.272Å 6 * Et Zn Et Cu P 1 2 Lewis acid Dual activation Lewis acid * H P 2 H P 2 Cl2 6a: = Et 6b: = i-pr 6c: = n-bu 6d: = i-bu 6e: = Ph

34 6a-e 6c 6e 6c Ph n-c 5 H 11 Ph Et Cu(Tf) 2 (1 mol%) 6c (1.2 mol%) Et 2 Zn (1.1 eq.), DMF Ph Ph 84%, >99% ee Cu(Tf) 2 (5 mol%) Et 6c (6 mol%) n-c 5 H 11 * Et Et 2 Zn (1.1 eq.), DMF 72%, 90% ee 7 7a: = Me 7b: = Et 7c: = Pr-i 7d: = Bu-n 7 7 7d Et (Eq. 1) (Eq. 2) Lewis base C 2 ' ' '' H Zn Et Zn H H Zn Zn H 2Et'Zn ''CH Et S S '' ' C 2 Lewis acid S: solvent = Et or Ph Cl CH CH PhB(H) 2, Et 2 Zn 7d (10 mol%), 0 C TBME PhB(H) 2, Et 2 Zn 7d (10 mol%), 0 C TBME H Ph Cl 93%, 95% ee H Ph 81%, 91% ee (Eq. 3) (Eq. 4)

35

36

37

38 Lewis 3-2-3

39

40 1. K. Miura, K. Tamaki, T. akagawa, and A. Hosomi, A ovel Catalytic System for the Mannich-type eaction of Silyl Enolates: Stereoselective Synthesis of β-aminoketones, Angew. Chem., Int. Ed. Engl., 39 (11), ; Angew. Chem., 112 (11), (2000). 2. H. Ito, T. Yajima, J. Tateiwa, and A. Hosomi, First Gold Complex-Catalysed Selective Hydrosilylation of rganic Compounds, Chem. Commun., (11), (2000). 3. K. Miura, T. akagawa, S. Suda, and A. Hosomi, Tandem Aldol-eduction eaction of Dimethylsilyl Enolates: A ew Method for Stereoselective Preparation of 1,3-Diols, Chem. Lett.,

41 (2), (2000). 4. K. Miura, S. kajima, T. Hondo, T. akagawa, T. Takahashi, and A. Hosomi, Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group: A ew Method for Stereoselective Synthesis of Disubstituted Tetrahydrofurans, J. Am. Chem. Soc., 122 (46), (2000). 5. K. Miura, H. Saito,. Fujisawa, and A. Hosomi, adical Cyclization of 1,6-Enynes Using Allylstannanes, J. rg. Chem., 65 (23), (2000). 6. H. Ito and A. Hosomi, ew Synthetic eactions Using Group 11 Metal Compounds as a Catalyst, J. Synth. rg. Chem., Japan, 58 (4), (2000). 7. K. Miura, T. Hondo, T. akagawa, T. Takahashi, and A. Hosomi, Acid-Catalyzed Cyclization of Vinylsilanes Bearing an Amino Group. Stereoselective Synthesis of Pyrrolidines., rg. Lett., 2 (3), (2000). 8. M. Hojo,. Sakuragi, Y. Murakami, Y. Baba, and A. Hosomi, Direct Generation of Thiomethylmanganese eagents and Their eactions with Electrophiles, rganometallics, 19 (24), (2000). 9. H. Ito, H. Yamanaka, T. Ishizuka, J. Tateiwa, and A. Hosomi, ew eactivity of a educing eagent Generated from a Copper(I) Salt and a Hydrosilane: Selective eduction of Ketones and lefins Conjugated with an Aromatic Group, Synlett, (4), (2000). 10. K. Miura, T. Hondo, T. Takahashi, and A. Hosomi, Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group. Benzyldimethylsilyl Group as an Effective Promoter and ovel Hydroxy Surrogate, Tetrahedron Lett., 41 (13), (2000). 11. H. Ito, H. Yamanaka, J. Tateiwa, and A. Hosomi, Boration of an α,β-enone Using a Diboron Promoted by a Copper(I)-Phosphine Mixture Catalyst, Tetrahedron Lett., 41 (35), (2000). 12. M. Hojo, Y. Murakami, H. Aihara,. Sakuragi, Y. Baba, and A. Hosomi, Iron-Catalyzed egioand Stereoselective Carbolithiation of Alkynes, Angew. Chem., Int. Ed. Engl., 40 (3), (2001);Angew. Chem., 113 (3), (2001). 13. M. Hojo, S. kabe,. Sakuragi, and A. Hosomi, Allyl- and Propargylchromium eagents Generated by a Chromium(III) Ate-type eagent as a eductant and Their eactions with Electrophiles, Chem. Commun., (4), (2001). 14. K. Miura, T. Takahashi, H. ishikori, and A. Hosomi, Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hemiacetal Group, Chem. Lett., (10), (2001). 15. J. Tateiwa and A. Hosomi, Pentacoordinate rganosilicate-catalyzed Michael Addition of β-keto Ester to 3-Buten-2-one, Eur. J. rg. Chem., 4 (8), (2001). 16. K. Miura, H. Saito, D. Itoh, T. Matsuda,. Fujisawa, D. Wang, and A. Hosomi, Allylstannylation of Carbon-Carbon and Carbon-xygen Unsaturated Bonds via a adical Chain Process, J. rg. Chem., 66 (10), (2001). 17. K. Miura,. Fujisawa, H. Saito, D. Wang, and A. Hosomi, Synthetic Utility of Stannyl Enolates as adical Alkylating Agents, rg. Lett., 3 (16), (2001). 18. K. Miura, H. Saito,. Fujisawa, D. Wang, H. ishikori, and A. Hosomi, Homolytic Carbostannylation of Alkenes and Alkynes with Tributylstannyl Enolates, rg. Lett., 3 (25), (2001). 19. M. Hojo, K. Sakata,. Ushioda, T. Watanabe, H. ishikori, and A. Hosomi, eductive Generation of Enolates Using Chromium(III) Ate-Type eagent as a eductant and eactions of the Enolates with Electrophiles, rganometallics, 20 (24), (2001). 20. K. Miura, K. otsuka, S. Suda, H. ishikori, and A. Hosomi, Lewis Acid-Catalyzed eductive Amination of Carbonyl Compounds with Aminohydrosilanes, Synlett, (10), (2001). 21. J. Tanaka and S. Kanemasa, Ab initio Study of Lewis Acid Catalyzed itrone Cycloaddition to Electron Deficient Alkenes. Does a Lewis Acid Catalyst Change the eaction Mechanism? Tetrahedron, 57 (5), (2001). 22. Y. Kohmura and T. Katsuki, Mn(salen)-Catalyzed Enantioselective C-H Amination, Tetrahedron Lett., 42, (2001). 23. B. Saito and T. Katsuki, Ti(salen)-Catalyzed Enantioselective Sulfoxidation Using Hydrogen Peroxide as a Terminal xidant, Tetrahedron Lett., 42 (23), (2001). 24. K. akama, S. Seki, and S. Kanemasa, A ew Synthetic Access to -Alkylated itrones through Lewis Acid-Catalyzed Conjugate Additions of Aldoximes, Tetrahedron Lett., 42 (38),

42 (2001). 25. T. Uchida and T. Katsuki, Cationic Co(III)(salen)-Catalyzed Enantioselective Baeyer-Villiger xidation of 3-Arylcyclobutanones Using Hydrogen Peroxide as a Terminal xidant, Tetrahedron Lett., 42 (39), (2001). 26. A. Miyata, M. Murakami,. Irie, and T. Katsuki, Chemoselective Aerobic xidation of Primary Alcohols Catalyzed by uthenium Complex, Tetrahedron Lett., 42 (40), (2001). 27. M. Murakami, T. Uchida, and T. Katsuki, u(salen)-catalyzed Asymmetric Sulfimidation Using Arylsulfonyl Azide, Tetrahedron Lett., 42 (40), (2001). 28. B. Saito and T. Katsuki, Mechanistic Consideration of Ti(salen)-Catalyzed Asymmetric Sulfoxidation, Tetrahedron Lett., 42 (47), (2001). 29. K. Miura,. Fujisawa, H. Saito, H. ishikori, and A. Hosomi, Intramolecular Carbostannylation via a adical Chain Process, Chem. Lett., (1), (2002). 30. K. Masutani,. Irie, and T. Katsuki, Asymmetric Cyclization via xygen Cation adical: Enantioselective Synthesis of cis-4b,9b-dihydrobenzofuro[3,2-b]benzofurans, Chem. Lett., (1), (2002). 31. M. Hojo, K. Sakata, X. Maimaiti, J. Ueno, H. ishikori, and A. Hosomi, Homoaldol and Aldol eactions from Common Enolates and xiranes: eaction of eductively Generated Chromium Enolates through Cationic earrangement, Chem. Lett., (2), (2002). 32. B. Saha, T. Uchida, and T. Katsuki, Highly Enantioselective Intramolecular Cyclopropanation of Alkenyl Diazo Ketones Using u(salen) as Catalyst, Chem. Lett., (8), (2002). 33. H. Shimizu, K. akata, and T. Katsuki, (Salen)ruthenium-Catalyzed Desymmetrization of Meso-Diols: Catalytic Aerobic Asymmetric xidation under Photo-Irradiation, Chem. Lett.,, (11), (2002). 34. T. Uchida, T. Katsuki, K. Ito, S. Akashi, A. Ishii, and T. Kuroda, ew Asymmetric Catalysis by (Salen)cobalt(III) Complexes (Salen= [Bis(salicylidene)ethylenediaminato]= {{2,2'-[ethane-1,2-diyl]bis[nitrilo-k]methylidene}bis[phenolato-]}(2-))) of cis-β Structure: Enantioselective Baeyer-Villiger xidation of Prochiral Cyclobutanones, Helv. Chim. Acta, 85 (10), (2002). 35. K. Miura, T. akagawa, and A. Hosomi, Lewis Base-Promoted Aldol eaction of Dimethylsilyl Enolates in Aqueous Dimethylformamide: Use of Calcium Chloride as a Lewis Base Catalyst, J. Am. Chem. Soc., 124 (4), (2002). 36. K. Itoh and S. Kanemasa, Enantioselective Michael Additions of itromethane by a Catalytic Double Activation Method (CDAM) Using Chiral Lewis Acid and Achiral Amine Catalysts, J. Am. Chem. Soc., 124 (45), (2002). 37. K. Miura, T. Hondo, S. kajima, T. akagawa, T. Takahashi, and A. Hosomi, 1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans, J. rg. Chem., 67 (17), (2002). 38. K. Miura, K. otsuka, S. Suda, H. ishikori, and A. Hosomi, Lewis Acid-Catalyzed eductive Etherification of Carbonyl Compounds with Alkoxyhydrosilanes, Synlett, (2), (2002). 39. S. Kanemasa, 1,3-Dipolar Cycloadditions and Enantioselective Catalysis, My Favorite rganic Synthesis, the Society of Synthetic rganic Chemistry, Japan, (2002). 40. A. Kamimura, Y. Kaneko, A. hta, K. Matsuura, Y. Fujimoto, A. Kakehi, and S. Kanemasa, Enantioselective Preparation of 3,4,5-Trisubstituted 4,5-Dihydroisoxazoles and Their Stereoselective Elaboration of 5-Side Chain, Tetrahedron, 58 (47), (2002). 41. S. Kanemasa,. Ueno, and M. Shirahase, itrone Cycloaddition eactions to α,β-unsaturated Carbonyl Acceptors Catalyzed by a Pinhole Lewis Acid Catalyst. Dramatic ate Acceleration and Improvement of egioselectivity and Diastereoselectivity, Tetrahedron Lett.,43 (4), (2002). 42. K. akama, S. Seki, and S. Kanemasa, Enantioselective Conjugate Additions of Aldoximes to 3-Crotonoyl-2-oxazolidinone and 1-Crotonoyl-3-phenyl-2-imidazolidinone Catalyzed by the Aqua Complex between,-dbfx/ph and Zinc(II) Perchlorate, Tetrahedron Lett., 43 (5), (2002). 43. T. Tanaka, B. Saito and T. Katsuki, Highly Enantioselective xidation of Cyclic Dithioacetal by Using a Ti(salen) and Urea Hydrogen Peroxide System, Tetrahedron Lett., 43 (18),

43 (2002). 44. A. Watanabe, T. Uchida, K. Ito, and T. Katsuki, Highly Enantioselective Baeyer-Villiger xidation Using Zr(salen) Complex as Catalyst, Tetrahedron Lett., 43 (18), (2002). 45. A. Miyata, M. Furukawa,. Irie, and T. Katsuki, Catalytic Aerobic xidation of Diols: Highly Efficient Synthesis of Lactols, Tetrahedron Lett., 43 (19), (2002). 46. M. Murakami and T. Katsuki, Chiral (C)u(salen)-Catalyzed Tandem Sulfimidation and [2,3]Sigmatropic earrangement: Asymmetric C- Bond Formation, Tetrahedron Lett., 43 (21), (2002). 47. K. mura, M. Murakami, T. Uchida,. Irie, and T. Katsuki, Enantioselective Aziridination and Amination Using p-toluenesulfonyl Azide in the Presence of u(salen)(c) Complex, Chem. Lett., 32 (4), (2003). 48. H. Shimizu and T. Katsuki, (Salen)ruthenium-Catalyzed Desymmetrization of Meso-Diols (2): Apical Ligand Effect on Enantioselectivity, Chem. Lett., 32 (6), (2003). 49. Y. Matsuoka,. Irie, and T. Katsuki, Enantioselective Addition of 2-(Trimethylsilyloxy)furan to Aldehydes Using Cr(salen) as Catalyst: Effect of Water on Enantioselectivity, Chem. Lett., 32 (7), (2003). 50. S. nitsuka, Y. Matsuoka,. Irie, and T. Katsuki, Highly Enantioselective Cr(salen)-Catalyzed eaction of 2-(Trimethylsilyloxy)furan and Aldehydes: Effect of Alcohol on Enantioselectivity, Chem Lett., 32 (10), (2003). 51. B. Saito and T. Katsuki, Asymmetric xidation of acemic 2-Substituted 1,3-xathianes, Chirality, 15 (1), (2003). 52. K. Miura, T. Takahashi, T. Hondo, and A. Hosomi, 1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing an Amino Group, Chirality, 15 (1), (2003). 53. M. Murakami, T. Uchida, B. Saito, and T. Katsuki, u(salen)-catalyzed Asymmetric Sulfimidation and Subsequent [2,3]Sigmatropic earrangement, Chirality, 15 (2), (2003). 54. S. Kanemasa, Catalyzed Asymmetric Dipolar Cycloaddition, Farumashia, (2003). 55. K. Miura, T. Takahashi, and A. Hosomi, Acid-Catalyzed Intramolecular Addition of a Hydroxy Group to Vinylgermanes, Heterocycles, 59 (1), (2003). (Special Issue for Professor Yuichi Kanaoka). 56. K. Miura, D. Wang, Y. Matsumoto,. Fujisawa, and A. Hosomi, egio- and Stereoselective Homolytic Hydrostannylation of Propargyl Alcohols and Ethers with Dibutylchlorostannane, J.rg. Chem., 68 (22), (2003). 57. K. Miura, J. Hayashida, T. Takahashi, H. ishikori, and A. Hosomi, Acid-Catalyzed Intramolecular Addition of a Carboxy Group to Vinylsilanes, J. rganometal. Chem., 686 (21), (2003). 58. S. Kanemasa, Catalyzed Enantioselective Conjugate Addition eactions of Strongly Coordinating ucleophiles, J. Syn. rg. Chem. Jpn., 61, (2003). 59. K. Miura and A. Hosomi, Stereoselective Synthesis of Substituted Cyclic Ethers and Amines by Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy or Amino Group, Synlett, (2), (2003). 60. H. ishikori,. Yoshihara, and A. Hosomi, ptically Active Lithium-Alkoxide Catalyzed Asymmetric eduction of Imines with Trimethoxyhydrosilane, Synlett, (4), (2003). 61. K. Ito, A. Ishii, T. Kuroda, and T. Katsuki, Asymmetric Baeyer-Villiger xidation of Prochiral Cyclobutanones Using a Chiral Cataionic Palladium(II) 2-(Phosphinophenyl)pyridine Complex as Catalys, Synlett, (5), (2003). 62. T. Miyazaki and T. Katsuki, b(salen)-catalyzed Sulfoxidation, Synlett, (7), (2003). 63. K. Ito, S. Akashi, B. Saito, and T. Katsuki, Asymmetric Intramolecular Allylic Amination: Straightforward Approach to Chiral C1-Substituted Tetrahydroisoquinolines, Synlett, (12), (2003). 64. A. Tashiro, A. Mitsuishi,. Irie, and T. Katsuki, ()u(salen)-catalyzed Aerobic xidation of o-hydroxybenzyl Alcohol Derivatives, Synlett, (12), (2003). 65. K. Miura, T. akagawa, and A. Hosomi, Magnesium Chloride-Promoted Michael Addition of Dimethylsilyl Enolates to α-enones, Synlett, (13), (2003). 66. K. Itoh, Y. deraotoshi, and S. Kanemasa, Enantioselective Michael Addition eactions of Malononitrile Catalyzed by Chiral Lewis Acid and Achiral Lewis Base Catalysts, Tetrahedron: Asymmetry, 14 (6), (2003).

44 67. B. Saha, T. Uchida, and T. Katsuki, Asymmetric Intramolecular Cyclopropanation of Diazo Compounds with Metallosalen Complexes as Catalyst: Structural Tuning of Salen Ligand, Tetrahedron: Asymmetry, 14 (7), (2003). 68. K. Itoh and S. Kanemasa, A ew Method for Enol Lactone Synthesis by a Michael Addition/Cyclization Sequence, Tetrahedron Lett., 44 (9), (2003). 69. Y. Tamura, T. Uchida, and T. Katsuki, Highly Enantioselective (C)u(salen)-Catalyzed Sulfimidation Using -Alkoxycarbonyl Azide as itrene Precursor, Tetrahedron Lett., 44 (16), (2003). 70. T. Uchida, Y. Tamura, M. hba, and T. Katsuki, Mechanism of Asymmetric Sulfimidation with -Alkoxycarbonyl Azide in the Presence of (C)u(Salen) Complex, Tetrahedron Lett., 44 (43), (2003). 71. K. Miura, M. Tojino,. Fujisawa, A. Hosomi, and I. yu, Cascade Carbonylation Methods Leading to β -Diketones and β -Functionalizedδ -Diketones, Angew. Chem., Int. Ed. Engl., 43 (4), (2004). 72. K. Miura and A. Hosomi, Development of ew eagents Containing Silicon and elated Metals and Application to the Practical rganic Synthesis, Bull. Chem. Soc. Japan., 77 (5), (2004). 73. K. mura, T. Uchida,. Irie, and T. Katsuki, Design of a obust u(salen) Complex: Aziridination with Improved Turnover umber Using -arylsulfonyl Azides as Precursor, Chem. Commun. (18), (2004). 74. S. Kanemasa, and K. Ito, Double Catalytic Activation with Chiral Lewis Acid and Amine Catalysts, Eur. J. rg. Chem., (23), (2004). 75. K. Miura,. Fujisawa, and A. Hosomi, Indium(III) Chloride-Promoted Intramolecular Addition of Allylstannanes to Alkynes, J. rg. Chem., 69 (7), (2004). 76. M. Shirahase, S. Kanemasa, and Y. deraotoshi, Chiral DBFX/Ph Complex- Catalyzed Enantioselective itrone Cycloadditions to α,β-unsaturated Aldehydes, rg. Lett., 6 (5), (2004). 77. U. Iserloh, Y. deraotoshi, and S. Kanemasa,.D. P. Curran, Synthesis of (,)-4,6-Dibenzofurandiyl-2,2'-bis(4-phenyloxazoline) (DBFX/Ph), A ovel Tridentate Ligand, rg. Synth., (80), (2004). 78. A. Watanabe, T. Uchida,. Irie, and T. Katsuki, Zr[bis(salicylidene)ethylenediaminato]-Mediated Baeyer-Villiger xidation: Stereospecific Synthesis of Abnormal and ormal Lactones, P. atl. Acad. Sci. USA, 101 (16), (2004). 79. S. Kanemasa, itrile xides, Sulfides, and Selenides, Sience of Synthesis, Three Carbon - Heteroatom Bonds, itriles, Isocyanides, and Derivatives, (19), (2004). 80. S. Kanemasa, itrile Imines, Sience of Synthesis, Three Carbon - Heteroatom Bonds, itriles, Isocyanides, and Derivatives, (19), (2004). 81. S. Kanemasa, itrilium Salts, Sience of Synthesis, Three Carbon - Heteroatom Bonds, itriles, Isocyanides, and Derivatives, (19), (2004). 82. S. Kanemasa, itrile Ylides, Sience of Synthesis, Three Carbon - Heteroatom Bonds, itriles, Isocyanides, and Derivatives, (19), (2004). 83. B. Saito and T. Katsuki, Zn(salen)-Catalyzed Asymmetric Alkynylation of Ketones, Synlett, (9), (2004). 84. K. Miura, Y. Yamada, M. Tomita, and A. Hosomi, Indium(III) Acetate-Catalyzed 1,4-eduction and eductive Aldol eactions of - Enones with Phenylsilane, Synlett, (11), (2004). 85. K. Matsumoto, A. Watanabe, T. Uchida, K. gi, and T. Katsuki, Construction of a ew Asymmetric eaction Site: Asymmetric 1,4-Addition of Thiol Using Pentagonal bipyramidal Hf(salen) Complex as Catalyst, Tetrahedron Lett., 45 (11), (2004). 86. M. Shirahase, S. Kanemasa, and M. Hasegawa, Improved Catalysis of itrone 1,3-Dipolar Cycloadditions by Solving the Aggregation Issue of the DBFX/Ph - Transition Metal Complexes, Tetrahedron Lett., 45 (21), (2004). 87. M. Hojo,. Ushioda, and A. Hosomi, Alkylation of acetals using manganate-bf 3. Et 2 mixed reagent, Tetrahedron Lett., 45 (23), (2004). 88. A. Watanabe, K. Matsumoto, Y. Shimada, and T. Katsuki, xovanadium(v)-catalyzed

45 Enantioselective Meerwein-Ponndorf-Verley Cyanation of Aldehydes Using Acetone Cyanohydrin, Tetrahedron Lett., 45 (33), (2004). 89. K. Ito, Y. Imahayashi, T. Kuroda, S. Eno, B. Saito, and T. Katsuki, Palladium-Catalyzed Asymmetric Tandem Allylic Substitution Using Chiral 2-(phosphinophenyl)pyridine Ligand, Tetrahedron Lett., 45 (39), (2004) Shibata, J. Kohno, K. Takai, T. Ishimaru, S. akamura, T. Toru, and S. Kanemasa, Highly Enantioselective Catalytic Fluorination and Chlorination eactions of Carbonyl Compounds Capable of Two-Point Binding, Angew. Chem. Int. Ed. 44 (27), (2005). 91. B. Saito and T. Katsuki, Synthesis of ptically Active C 1 Symmetric Al(salalen) Complex and Its Application to Catalytic Hydrophosphonylation of Aldehydes, Angew. Chem. Int. Ed. 44 (29), (2005). 92. K. Matsumoto, Y. Sawada, B. Saito, K. Sakai, and T. Katsuki, Construction of ovel Pseudo Heterochiral- and Homochiral Di-µ-oxo Ti(Schiff-base) Dimers and Enantioselective Epoxidation Using Aqueous Hydrogen Peroxide, Angew. Chem. Int. Ed. 44 (31), (2005). 93. Y. Shimada and T. Katsuki, Cr(salen)-catalyzed Asymmetric Addition of Allylstannane to Aldehydes, Chem. Lett. 34 (6), (2005). 94. H. Shimizu, S. nitsuka, H. Egami, and T. Katsuki, uthenium(salen)-catalyzed Aerobic xidative Desymmetrization of meso-diols and Its Kinetics, J. Am. Chem. Soc. 127 (15), (2005). 95. K. Miura, D. Wang, and A. Hosomi, Highly Diastereoselective Hydrostannylation of Allyl and Homoallyl Alcohols with Dibutyl(trifluoromethanesulfoxy)stannane, J. Am. Chem. Soc, 127 (26), (2005). 96. K. Miura, D. Wang, and A. Hosomi, Highly egio- and Stereoselective Hydrostannylation of Propargyl Alcohols and Ethers Using Dibutylchlorostannane and Lithium Chloride, Synlett, (3), (2005). 97. K. Miura, D. Wang, Y. Matsumoto, and A. Hosomi, Highly egio- and Stereoselective Hydrostannylation of Alkynols with A ew Lewis Acidic Hydrostannane, rg. Lett., 7 (3), (2005). 98. K. Itoh, M. Hasegawa, J.Tanaka, and S. Kanemasa, Enantioselective Enol Lactone Synthesis under the Double Catalytic Conditions, rg. Lett., 7(6), (2005). 99. K. Miura, T. akagawa, and A. Hosomi, Metal Chloride-Promoted Aldol eaction of Dimethylsilylesters with Aldehydes and Ketones, Synlett, (12), (2005) K. Miura, K. otsuka, and A. HosomiSynthetic adical eactions Using Dibutylchlorogermane and Dibutylethoxygermane as adical MediatorsSynlett, 2005 in press 101. H. Egami, H. Shimizu, and T. Katsuki, Aerobic xidation of Primary Alcohols in the Presence of Activated Secondary Alcohols, Tetrahedron Lett., 46 (5), (2005) K. Ito, S. Eno, B. Saito, and T. Katsuki, Enantioselective conjugate addition of diethylzinc to acyclic enones using a copper phosphino-phenol complex as catalyst, Tetrahedron Lett. 46 (23), (2005) K. Ito, Y. Tomita, and T. Katsuki, Enantioselective phenyl transfer to aldehydes using 1,1 -bi-2-naphthol-3,3 -dicarboxamide as chiral auxiliary, Tetrahedron Lett., 46 (36), (2005) H. Egami, S. nitsuka, and T. Katsuki, A reasonable explanation for the mechanism of chemoselective aerobic oxidation of alcohols using ()u(salen) complex as catalyst, Tetrahedron Lett., 46 (36), (2005) F. no, S. Kanemasa, and J. Tanaka, eusable nano-sized chiral bisoxazoline catalysts, Tetrahedron Letters, 46 (44), (2005).

46

47 β

48 Cryptomoscatone E2 Highly Enantioselective Baeyer-Villiger xidation Using Metallosalen Complexes of CisβStructure as Catalyst Cisβ (Salen)ruthenium-Catalyzed Desymmetrization of Meso-Diols: Catalytic Aerobic Asymmetric xidations, 8th International Conference on Chemistry of Antibiotics and elated Microbial Products 2-(Trimethylsilyloxy)furan

49 GranShip (itrosyl)(salen)ruthenium-catalyzed asymmetric aerobic oxidation: desymmetrization of meso-diols The 15th International Symposium on ChiralityGranShip Baeyer-Villiger ()u(salen)-catalyzed Aerobic xidative Desymmetrization of meso-diols Meerwein-Ponndorf-Verley

50

51 1. S. Kanemasa, Enantioselective 1,3-Dipolar Cycloaddition eactions Catalyzed by Tolerant Chiral Lewis Acid Catalysts. itrone and itronate Cycloaddition eactions, 18th InternationalCongress of Heterocyclic Chemistry, Yokohama, July 30, S. Kanemasa, Enantiomer Synthesis by a Dual Activation Method, rganic Seminar at orth Dakota State University, USA, ctober 24, S. Kanemasa, How Powerful is the ew Methodology Using both Lewis Acid and Base Catalysts? Dual Activation Method in Enantioselective Michael eactions, Synthetic Seminar in Molecumetics, USA, ctober 26, S. Kanemasa, Michael Additions by Use of Chiral Lewis Acid and Amine Catalysts, 9th ational rganic Symposium Trust - India/Japan Joint Meeting, India, December 12-16, S. Kanemasa, Chiral Lewis Acid-Catalyzed Enantioselective 1,3-Dipolar Cycloadditions of itrones, itronates, and Diazoalkanes, 2nd CIMS/PSTECH International Symposium, Pohang, January 1-February 4, S. Kanemasa, Lewis Acid Catalyzed Amine Conjugate Additions Giving Enantiomers of β-amino Acid Derivatives, LG esearch Institute Seminar, Daejeon, Korea, April 18, S. Kanemasa, Enantioselective 1,3-Dipolar Cycloadditions of itrones to Monodentate Acceptors, CMDS/ KIST Seminar, Daejeon, Korea, April 18, S. Kanemasa, How Effective Are the Enantioselective eactions by Use of both Acid and Base Catalysts? Annual Meeting of Korean Chemical Society (KCS Meeting), Seoul, Korea, April 20, S. Kanemasa, Enantioselective Michael Additions by the Catalytic Double Activation Method, Special Seminar at Arhus University, Denmark, August 20, S. Kanemasa, Chiral ickel(ii) or Zinc(II) Complex Catalyzed Enantioselective itrone Cycloadditions toαβunsaturated Aldehydes, Special Seminar at Arhus University, Denmark, August 21, S. Kanemasa, ew eactions for Enantiopure Heterocycles under Double Catalytic Conditions 2003 Gordon esearch Conference / Heterocyclic ChemistrySalve egina Universityew Port, IUSA 19. S. Kanemasa, Double Catalytic Enantioselective Michael Addition eactions Producing Enol Lactones, 2003 Gordon esearch Conference/Heterocyclic Compounds, USA, July 10, 2003.

52 21. S. Kanemasa, Double Catalytic Activation Method vs Single Catalytic Method. Which is more Useful? Special rganic Seminar at orth Dakota State University, Fargo, D USA, August 8, S. Kanemasa, Enantioselective Michael Additions through Double Catalytic Activation Using Chiral Lewis Acid and Amine Catalysts, 19th International Congress of Heterocyclic Chemistry, Colorado State University, Fort Collins, Colo., USA, August 11, Shuji Kanemasa, ickel(ii) Ion-Catalyzed Enantioselective Michael Addition eactions - Double to Single Catalytic Activations, International Symposium on Integrated rganic Synthesis, Hyogo, Awaji Yume-Butai International Congress Center, July 03-5, Shuji Kanemasa, Masayuki Hasegawa, Catalytic Enolization with Metal Acetates in Alcohols and Enantioselective Michael Additions under Multi Activation Conditions, 20th International Congress of Heterocyclic ChemistryPalermo, Italy, July 31-August 5, α

53 α,β α,β

54 αβ 1. A. Hosomi, ew Developments in rganic Synthesis Using rganometallic Compounds, University of California, San Diego, La Jolla, USA, March 27, A. Hosomi, ew Developments on Highly Coordinate rganometallic Compounds in rganic Synthesis, The 11th International Symposium of Fine Chemistry and Functional Polymers, Hailar, Inner Mongolia, China, Preprint p.16, July 28-31, A. Hosomi, Highly Coordinate rganometallic Compounds in rganic Synthesis, Institute of Chemistry, The Chinese Academy of Sciences, Beijing, China, August 4, A. Hosomi, ew Developments in rganic Synthesis Using rganometallic Compounds, Frontier in rganic Chemistry, Los Angels, USA, April 23, A. Hosomi, ew Developments in rganic Synthesis Using rganometallic Compounds, Moscow State University, Moscow, ussia, July 22, A. Hosomi, Highly Coordinate rganosilicon Compounds in rganic Synthesis, Moscow State University, Moscow, ussia, July 23, 2002.

55 9. A. Hosomi, ew Developments in rganic Synthesis Using rganometallic Compounds, University of München, München, Germany, December 21, A. Hosomi, Highly Coordinate rganosilicon Compounds in rganic Synthesis, Technische Hochschule, Dresden, Dresden, Germany, December 27, Seiji Mori, Hajime Ito, and Akira HosomiTheoretical Studies on Formation of CuH/AuH with Hydrosilanes and Subsequent eduction of Carbonyl Compounds 14th International Symposium on Homogeneous Catalysis, July 10-11, Munchen, German, 14th International Symposium on Homogeneous Catalysis (ISHC-14).

56 α,β

57

58 K. Masutani, T. Uchida,. Irie, and T. KatsukiAsymmetric Aerobic xidative Cyclization Catalyzed by (Salen)ruthenium Complexes, 18th International Conference of Heterocyclic Chemistry Mn(salen)-Catalyzed Enantioselective C-H Amination Diels-Alder Cryptomoscatone E2

59 8. T. Uchida, A. Watanabe, K. Ito and T. Katsuki, Enantiotopos Control in Baeyer-Villiger xidation with a Hydrogen Peroxide and Metallosalen of cisβstructure System. 8th Symposium: Activation of Dioxygen and Homogeneous Catalytic xidation, Atlanta, Georgia, USA, June 6, β Baeyer-Villiger Baeyer-Villiger Baeyer-Villiger Biswajit Saha Asymmetric Intramolecular Cyclopropanation Using Metallosalen Complexes as Catalyst, 8th International Conference on Chemistry of Antibiotics and elated Microbial Products (C)u-salen 18.

60 ()-Carnegine Zr(salen)-Mediated Enantiospecific Baeyer-Villiger xidationthe inth International Kyoto Conference on ew Aspects of rganic Chemistry Highly enantioselective (C)u(salen)-catalyzed sulfimidationthe inth International Kyoto Conference on ew Aspects of rganic Chemistry Enantioselective 1,4-Addition of Thiol with Pentagonal Bipyramidal Hf(salen) as CatalystThe inth International Kyoto Conference on ew Aspects of rganic Chemistry ew obust u(salen) Complex Allows for Highly Enantioselective itrene Transfer eactions (Aziridination and C-H Amination) Using Azide Compounds as itrene Precursors with emarkably Improved T IUPAC 15 th International Conference on rganic Synthesis Study on uthenium(salen)-catalyzed Asymmetric Aerobic xidation: Desymmetrization of meso-diolsiupac 15 th International Conference on rganic Synthesis Highly Topos-Selective and Enantiospecific Baeyer-Villiger eaction Using Zr(salen) Complex as CatalystIUPAC 15 th International Conference on rganic Synthesis Asymmetric Aziridination Using Azide Compounds as itrene Precursor in The Presence of obust u(salen) complex

61 Asymmetric Alkynylation of Ketones Using Zn(salen)complex as CatalystThe 16th Japan-Korea Joint Seminar for Young rganic Chemists Cr(salen)-Catalyzed Mukaiyama-Aldol eaction: Enantioselective Construction of δhydroxyβketo Ester DerivativesThe 16th Japan-Korea Joint Seminar for Young rganic Chemists Asymmetric Aziridination Catalyzed by obust u(salen)(c) Complexes with Azide Compounds as itrene Precursor 12th International Conference on Boron Chemistry Titanium-Mediated Enantioselective Epoxidation with Hydrogen Peroxide5th World Congress on xidation Catalysis Asymmetric Aziridination Catalyzed by obust u(salen)(c)complexes with Azide Compounds as itrene precursor Asymmetric Hydrophosphonylation of Aldehydes Catalyzed by ew ptically Active AI(salalen) Complex µ

62 . Yoshitake and S. Kanemasa, Enantioselective Conjugate Addition of Azide to αβunsaturated Carbonyl Compounds Catalyzed by Chiral Lewis Acids K. Miura,. Fujisawa, and A. HosomIndium(III) Chloride-Promoted Intramolecular Addition of Allylstannanes and Allylsilanes to Alkynes M. Tojino, I. yu, K. Miura,. Fujisawa, and A. HosomiStannyl Enolates-Mediated Carbonylative Tandem adical eaction for the Synthesis of Functionalized Diketones M. Hojo,. Sakuragi, and A. Hosomi Synthesis of Dihydrofurans and Methylenetetrahydrofurans by xymanganation of Alkynyl Alkoxides

63 eactions of Alkenes with Aldehydes and Acetals Catalyzed by a Platinum Catalyst β

64 β

65 1. K. Matsumoto, Y. Sawada, B. Saito, K. Sakai, and T. Katsuki, Construction of ovel Pseudo Heterochiral- and Homochiral Di-µ-oxo Ti(Schiff-base) Dimers and Enantioselective Epoxidation Using Aqueous Hydrogen Peroxide, Angew. Chem. Int. Ed. 44 (31), (2005). 2. A. Watanabe, T. Uchida,. Irie, and T. Katsuki, Zr[bis(salicylidene)ethylenediaminato]-Mediated Baeyer-Villiger xidation: Stereospecific Synthesis of Abnormal and ormal Lactones, P. atl. Acad. Sci. USA, 101 (16), (2004).

66 Armin de Meijere University of Göttingen Paul H. Knochel University of München liver eiser University of egensburg Uli Kazmaier University of the Saarland Dan Yang University of Hong Kong Patrick J. Walsh University of Pennsylvania ( )

67 Welcome to The Symposium on ew-generation Catalysts for ew-generation Synthesis Sponsored by Core esearch for Evolutional Science and Technology (CEST) Japan Science and Technology Agency (JST)

68

69

70

71

72

73

74