“Wako Organic Square”Vol. 46
Contents
1.2. Schotten Baumann 1955 NIN DCC DCCD DCCI 9 R N C N R DCC
3. Wako Organic Chemical News 1 Luche 2 3 anti Markovnikov Wako Organic Chemical News e
4. DPPA OC O OPh R_ Oo Oph 7 Il R Ns a O OE 55 RR NH PhO Ns3 R_ o gt Soph 6 DPPA Na R 2 DPPA Curtius BOP DPPA
5. R COX HX X HX 1 RRNH CD HO N 3 TA N A 2 TR R FR H X O Re 1 N R TH R R R R base gt gt gt
6. Smopex QO 102 FG Pd Pt Fe Cu Ni OH 105 FG N All PGM 111 FG F PGMs CU SH QO 234 FG 9H Pd PtRh Ru IrAg Cu Sn QO PGM No New 351 31511 5g 4 000 New 359 31512 Smopex 102 FG Acrylic Acid 25g 9 500 New 357 31513 100g 28 000 New 358 31521 5g 4 000 New 356 31522 Smopex 105 FG Vinylpyridine 25g 10 000 New 354 31523 100g 30 000 New 355 31531 5g 4 000 New 353 31532 Smopex 111 FG Styrylthiol 25q 9 500 New 351 31533 100g 28 000 New 352 31541 59g 4 500 New 350 31542 Smopex 234 FG Mercaptoethylacrylate 25g 11 000 New 358 31543 100g 33 000 Smopex Johnson Matthey Plc UK K K QuadraSil OWako QuadraSil
7. QuadraSil 10 QuadraSil AP MP sl S MTU TA NH PH CD No 354 12561 352 12562 357 11912 355 11913 354 13041 352 13042 356 12521 354 12522 350 13021 358 13022 QuadraSil AP QuadraSil MP QuadraSil MTU QuadraSil TA QuadraSil PHI Pd Ru Rh Cu Fe Co Ni Pd Pt Rh Ru Cu Pb Ag Hg Pd Rh Cu Ru Pb Fe Co Pd Rh Co Cu Fe Ru Cd Au V Zn Pt Rh Pd Cu Fe Co Ni 59 5 000 AminopropyI 25o 14 000 MercaptopropyI 29 ICM NIS 100g 45 000 5d 7 000 MethylIthiourea 25g 26 000 a 59 5 000 Triamine 25g 14 500 5d 7 000 Phenolicimine 25g 23 000 QuadraSil Johnson Matthey Plc UK K K Wako Organic Chemical News Wako Web
8. R O N 4 4 O NH N N HOBt OH R 2 3 N LL LR RR NH R NN N E R O R N CN R 1 R OH HOBt HOBt 7 CH 1 A HOAt 7 1 N N OH HOAt DPPA 1972
9. 1 1985 16 IYV 2005 2 Am Chem Soc 77 1067 1955 3 Og CZez7 26 2525 1961 4 Chem Ber 103 788 1970 5 Am Chem Soc 115 4397 1993 6 31 666 1973 7 Tetrahedron 36 3413 1980 8 Tetrahedron Lett 31 205 1990 9 Tetrahedron 60 2447 2005 10 Chem Eur 15 9404 2009 11 Tetrahedron Lett 40 5327 1999 Tetrahedron 57 1551 2001 Wako No OMe DA pp 4 6 Dimethoxy 1 3 5 triazin 2 yl 2 octoxy 2 oxoethyl Nn 19 17 000 ef Jimethylammonium Trifluoromethanesulfonat A 046 32753 IMe Yla O IU UO O T1etT1aT1eSUITO 14tG MeO N A Y CaH 7 59 65 000 ON 4 4 6 Dimethoxy 1 3 5 triazin 2 y 4 methyImorpholinium 29 00 045 32402 Ref Chloride n Hydrate I 25g 21 500 043 3
10. 2 4 6 1 3 5 CDMT CDMT CDMT N DMT MM 7 OMe CI OMe 0 N 3 v v OMe OMe CDMT DMT MM DMT MM
11. Table 2 Scheme 1 M 9 0 Square No 43 p14 p15 2 Table 1 2 Pd dba 1 mol O Ph PH 6 mol2 Ys a nau Pt mV N base 3 eq N 1 5 eq Dioxane 110 C 20 h oO _B oH sem pin VB N Ph BFak N N O N pase KF 0 yield 0 yield 6 yield 0 yield base NaOtBu 8 yield 49 yield 15 yield 10 yield Table 2 1 Pd catalyst 3 mol SL Ligand L Cul HetAr B 9 Br Ar EE HetAr Ar O DMF 22 h 2 3 eq product yield temp O OO 7w CR Ko 90 80 C 88 80 C 70 80 C 99 80 C 89 80 C cat Pd OAc cat PdClsdppp cat Pd OAc 2 cat PdClsdppp 2 Mol cat Pd OAc 2 L PPh Nal 2 eq
12. Water Soluble Carbodiimide WSCD NA NS cs NN N N DCC WSCD 1 1 HOBt WSCD HOBt
13. RN SE Castro 7 BOP HMPA HOBt NMe2 MesN 1 MeN bo N N N PFe BOP BOP DPPA A CE HMPA 9 00 PyBOP BOP i BOP O 1 N N N N HBTU A
14. 2L ChiralTLCP IE 2L ChiralTLCY IE CHIRALFLASH IE NAS 2L ChiralITLC IE 0 7 a O TLC Wieland Miescher ketone WMK CHIRALFLASH IE n Hexane Ethanol 60 40 VV 12mL min RR T 10mg 20mg UV254nm 10mg 20mg 0 0 05 0 1 0 15 0 2 0 10 20 30 40 Time min Wieland Miescher ketone WMK No 2L ChiralTLC 4types 8102101 514 pChiral TLc9 IAC IDAF 1 DOWX20om NT oY 388 02111 80T2A 2L ChiralTLC IA 10cm x 20cm 2 45 000 385 02121 83T2A 2L ChiralTLC 1C 10cm x 20cm 2 45 000 382 02131 84T2A 2L ChiralTLC ID 10cm x 20cm 2 45 000 2L ChiralTLC
15. W J Hehre 2 625 Spartan Student Edition ee Student Ed Spartan Eo W J Hehre A J Shusterman J E Nelson 4 725 HE mkkp a 21 200 1 WAVEFUNCTION INC 2 100 Spartan Flash CD ROM G TK Wako Organic Sgquare No 46 13
16. siyaku com httpr www siyaku Com Siyaku com 20183 11 Siyaku com http www siyaku com Lz 540 8605 2 TEL 06 6203 1788 103 0023 5 13 TEL 03 3270 8243 TEL 0O92 622 1005 TEL OR2 285G638 TEL O52 772 0788 TEL OMH6G 29 0351 TEL O29B5RL2278 TELI OB2 2929 3072 TEL 0l1 271 0285 URL http www wako chem co jp E mail labechem tec wako chem
17. B BF4 TBTU Nt N N NN XN N N O N PF N A O form B N form HOAt HATU TATU EN N N ST 2 3 N gt N eeF N BF4 O O HATU TATU 2009 COMU MN HATU HOBt QO N PTY COMU
18. SMAP TRIP Silica SMAP Rh C H Silica SMAP Silica TRIP C H 2 a 0 0 0 O O 0 SI g O O O S O O 9 O 1 SiO gt SiO Silica SMAP Silica TRIP C H Silica SMAP Rh OH cod a Rh 0 5 mol N O v _Silica SMAP RhL 1 1 B THF rt 1 h O 103 H NMR yield C H Silica TRIP Rh OMe cod s O O Rh 0 5 mol Me gt n Me Me N_ Bpin Me Silica TRIP Rh L 1 1 Me DIn B B DIn hexane 60 C 1h 126 H NMR yield No 197 17451 1 18 000 Silica SMAP 1
19. e e Mail org wako chem co jp Ei nnWiakn rl mh hi Fl FS OE CP Ma Em Im PH Chermniel hr CE TT Ljrlm shm 1 Tum EE EE TM EP i WP i TE w 1 EE BHT L 0 rh EHIME 1 np GE LN 1 E Or m IE WE HBH leg tH OH 1 LCTH 1Wm oe Ss kanH 1 Oy I F lm
20. 1 SAPd 0 5 mmol 1 mmol SAPd 1 2 SAPd 3 SAPd MM SMO NM09 K CO 2 0 eq Ethanol 3ml 3 mL Ar 80 C 12 h CI 10 aipnbs 0 5 mmol 1 5 ed yield gt 99 Buchwald Hartwig O O SAPd Catalyst KO t Bu 1 4 ed N KJ i Xylene 1 mL J 4 6 Ar 130 CC 7 h yield 0 32 mmol 1 2 eq 93 1st 91 10th SAPd SAPd lm No 190 17321 SAPd Catalyst 12 x 14mm 1 85 000 DD 0 1 Hoshiya N Shuto S Arisawa M Adv Synth Catal 353 743 2011 2 Al Amin M Honma T Hoshiya N Shuto S Arisawa M Adv Synth Catal 354 1061 2012 3 Hoshiya N Shimoda M Yoshikawa
21. Wakosil 50NH HC Wako Wakosil Wakosil 50NH HC WakosiP 50NH s HC N6 239 02671 231 02675 239 02311 231 02315 Wakosil 50NH HC WakosiP 50NHz HC Wakogel 50NHz Wakosil 50NHz HC Wakogel 50NHz LC Conditions gt Column NHs HC Type L Eluent n Hexane IPA 90 10 v v Flow rate 20mL min Detection UV254nm Sample 2 4 6 Trimethylpyridine 4 Dimethylaminopyridine No 291 34541 297 34543 14g 25mL 295 34561 291 34563 34g 70mL 292 34571 298 34573 50g 100mL 299 34581 295 34583 110g 200
22. USB EMS Macintosh 2013 12 Intel or AMD only InteLbased Macintosh only Linux Windows Vista 7 or 8 OS X 10 6 10 7 or 10 8 Spartan 14 for Linux Parallel Suite 2GB RAM per core 2GB RAM per core Spartan 14 for Windows Windows 7 8 60GB disk space or higher 60GB disk space or higher Standard Parallel Suite 2 Parallel Suite SSPD SMD NANT ME SDartan14 1 Year Maintenance for Co
23. Lurha lmhHH FM 1 El 1 PO 1 1 Fi RE rd im mmmdrobrrrmEm Pr ET Et T ieEH rg TF EE N SDartan 14 NN Wavefunction Spartan 2D 2D iSpartan 2D 3 Spartan 14 Parallel Suite 2 IiSpartan A
24. w Schotten Baumann Schotten Baumann 1880 2 Wako
25. S Br Br PhN L Pd catalyst y PhoN GS B QO Cul 4 Pyridine cyclic trlolborate S 2 5 Chloropyridine cyclic triolborate Lithium Salt Li Cig 1g 26 000 DMF 80 C 1 5h Sodium Salt Ne O O Ref 1g 9 000 5g 31 000 3 Pyridine cyclic triolborate Potassium Salt K 0 160 23771 166 23773 2 Pyridine cyclic triolborate Lithium Salt 9 a ea FE 163 23761 1g 8 000 169 23763 5g 26 000 161 23762 25g 78 000 2 5 Fluoropyridine cyclic triolborate Lithium Salt O F Z _g SLO N 0 167 23781 035 21411 163 23783 1g 9 000 5g 30 000 3 Quinoline cyclic triolborate Potassium Salt O N O 2 6 MethoxyDyridine cyclic triolborate Lithium Salt i Op N G 2 6 Fluoropyridine cyclic triolborate Lithium Sal Li O Ref Ref F Ref MeO Ref 066 05721 1g 28 000 060 05621 1g 21 000 1137 16311 19 18 000 175 00681 1g 18 000 066 05623 5g 85 000 133 16313 _ 5g 73 000 171 00683 5g 63 000 2 Furan cyclic triolDorate 2 hiophene cyclic 2 5 Methylthiophene cyclic 2 5 Chlorothiophene cyclic SOdium Salt triolbDorate Sodium Sal triolDorate Sodium Salt triolDorate Sodium Salt Na NE NT NM ye Ce 9 A Ref 0 FE 0 EF 0 FE 0 063 05611 1g 12 000 204 17611 1g 10 000 130 17401 1g 18 000 033 22811 1g 21 000 069 05613 5g 43 000 200 17613
26. 30 SDartan Student Edition 50 License Pack Windows 50 005 00550 SXSU DW50 Macintosh Windows SDartan 14 Parallel Suite 1 Year Maintenance for Education Windows 14 1 1 228 000 Spartan J Spartan 14 2014 3 3 Spartan 14 Spartan Spartan 3 SpartanModel W J Hehre 5 250 bio SpartanModel Spartan
27. H Yamashita Y Shuto S Arisawa M Am Chem Soc 132 7270 2010 K K Raf 2 10 F 20D BO 1 1 T HI HT 1 EZ
28. 2L ChiralTLCY IE 2013 10 CHIRALFLASH IE TLC 2L ChiralTLC IE 2 UV UV 2L ChiralTLC IE IE 3 5 w lx 5 IT TFTWT w SS ST TL TL EF 1 2L ChiralTLCY IE TLC 2L ChiralTLCY IE CHIRALFLASHY IE
29. 54 000 No 163 07543 59 5 000 165 07542 pg Palladium Activated Carbon Pd 5 25g 17 000 167 07541 100g 55 000 161 15273 59 5 500 163 15272 Palladium Activated Carbon Pd 10 25g 18 500 165 15271 100g 59 000 160 13881 Palladium Barium Carbonate Pd 5 10g 8 500 163 21441 1g 4 000 169 21442 ra ac mAealec Carbon Ethylenediamine Complex 5g 13 500 Pd 3 5 6 5 161 21442 250 48 000 167 24261 Palladium Hydroxide on Activated Carbon 39 7 800 165 24262 Pd 20 wetted with ca 50 water a 25g 30 000 160 24131 Palladium Activated Carbon DiphenyI Sulfide Complex lg 5 000 166 24133 Pd8 5 11 5 wetted with ca 50 water 5d 15 500 031 21371 200mg 7 000 Cinchonidine modified Palladium Activated Carbon 037 21373 Re 0 1g 24 000 1 Crabtree R H Davis M W Org Chem 51 2655 1986 2 Hong A Y Stoltz B M Angew Chem Int Ed 51 9674 2012 K OS Sllica SMAP Silica Supported Silicon Constrained Monodentate TrialkylphosDhine Silica TRIP Silica Supported Triptycene Type Phosphine Wako
30. co jp 0120 052 099 0120 052 806 OJBW Wako Ovwerseas Offices w Wako Chemicals USA_Inc DM Head Offica Fichmmgnd VA TEL 1 BO4 714 1920 http wwmw waknusa COm Los Angeles Sales Offices CA TEL 1 949 679 1700 E mail org wako chem co jp Boston Sales Offices MA TEL 1 617 354 6772 URL http Www wako chem co jp WUaho Charmica5 GmbH Europear WCe TEL 9 2131 311 0 hHP www wakp chemicals de 13Z08 2 oiR
31. 2403 DMT MM cr Lo ao 1009 63 000 No QO 099 22512 Ref MM Carbonyldiimidazole lt 29 0 031 22611 CDU 250g 36 000 No 021 17 42 023 17 41 026 17731 024 17732 038 22621 034 22623 036 22622 Ref Ref Ref 1 Benzotriazol 1 yloxytris dimethylamino phosphonium Hexafluorophosphate BOP 1 Benzotriazol 1 yloxytripyrrolidinophosphonium Hexafluorophosphate Chlorotripyrrolidinophosphonium Hexafluorophosphate PyClop No 041 32541 04 32543 044 32911 042 32912 190 16601 196 16603 1998 16602 038 22481 036 22482 034 22483 O 3 4 Dihydro 4 0x0 1 2 3 benzotriazin 3 yl Ref N N N N tetramethyluronium Tetrafluoroborate TDBTU 3 Diethoxyphosphoryloxy 1 2 3 benzotriazin 4 3 one DEPBT r O N Succinimidyl N N N N tetramethyluronium Ref HT Ref Tetrafluoroborate TSTU 1 Cyano 2 ethoxy 2 oxoethylidene amino oxy 4 morpholinomethylenejdimethylammonium Hexafluorophosphate No 040 01682 042 01681 044 01685 042 32892 044 32891 046 32895 No 044 32531 040 32533 042 32532 081 097 1 083 09775 M Dicycl
32. 5g 36 000 136 17403 5g 68 000 039 22813 5g 85 000 1 Billingsley K L Buchwald S L Angew Chem Int Ed 47 4695 2008 2 Yamamoto Y Heterocycles 85 799 2012 3 Yu XX Q Yamamoto Y Miyaura N Chem Astan 3 1517 2008 4 Yu X Q Yamamoto Y Miyaura N Synlett 994 2009 NPhz 81 2 6 Chloropyridine cyclic triolborate Lithium Salt Ref CI 030 21461 036 21463 1g 20 000 5g 82 000 3 6 9 Hexylcarbazole dicyclic triolborate Dipotassium Salt Ref RNN 080 09121 1g 10 000 086 09123 5g 36 000 5 2 2 bithiophene cyclic triolDorate Sodium Salt S So FE F 021 18401 1g 18 000 027 18403 5g 69 000 T M Smopex Wako Smopex 0
33. 93 17459 IO 5g 70 000 194 17461 1 15 000 Silica TRIP 190 17463 SO 5g 60 000 1 Kawamorita S Miyazaki T Ohmiya H Iwai T Sawamura M Am Chem Soc 133 19310 19313 2011 2 Kawamorita S Miyazaki T Iwai T Ohmiya H Sawamura M Am Chem Soc 134 12924 12927 2012 T S Wako 4 CB 2 2 2 Table 1 Table 3 Ns
34. DECEMBERH 01 SiMes Si O O I Si Si PSro po 1 SIO2 P 7 Silica SMAP 02 07 10 10 16 14 14 15 12 11 Organic Square Silica SMAP Silica Supported Silicon Constrained Monodentate TrialkyIphosphine Silica TRIP Silica Supported Triptycene Type Phosphine Smopex QuadraSil SAPd Sulfur Modified Au Supported Pd Catalyst Crabtree Wakosil 50NH HC NH2 HC 2L ChiralTLC IE Spartan 14 Wako Organic Chemical News Wako
35. L PPh Cul 0 2 eq L PPhs Cul 0 2 eq Cul 0 2 ed Cul 0 4 eq Ar TfO Ar Cul 0 4 eq CI Ar wa a 4 _ cozMe N N lt gt NO MeO 8596 80 C 78 80 CO 77 80 C 86 100 C cat PdClsdppp 2 mol cat PdClsdppp 2 mol cat eG moI cat Pd OAC Cul 0 2 eq Cul 0 2 eq Cul 0 1 eq L PPhs Cul 0 4 ed Ar B OH Table 3 H O Ar H B OH 3 pH 6 7 temp om len LTod B OH Yaiom K K 1 5 500 550 000 7 050 910 000 Ar Th 90 68 5 C 68 5 C 68 5 C 68 5 C 7 100 850 000 70 70 C 029 17221 Organic Square No 40 p20 Scheme 1 2 2 4 i THF H O Not obtained Ph N B pin 9 SS toluene H O 31 lt solvent reflux 7 h A 43 S S
36. New 380 03891 85T2A 2L ChiralTLC IE 10cmx20cm 2 45 000 389 02141 86T2A 2L ChiralTLC IF 10cm x 20cm 2 45 000 5 NOM mm mm Cu m g 306 95801 80M73 CHIRALFLASHY IA 30 100 20 40 300 000 303 95811 83M73 CHIRALFLASHY IC 30 100 20 40 300 000 309 99431 84M73 CHIRALFLASHY ID 30 100 20 40 300 000 386 02531 85M73 CHIRALFLASHY IE 30 100 20 40 300 000 CHIRALFLASH 385 01261 86M73 CHIRALFLASH F 30 100 20 40 300 000 2L ChiralTLC HP http www daicelchiral com CPI 0120 780 104 e mail chiral jp daicel com GTK 15 SAPd Sulfur Modified Au Supported Pd Catalyst Wako Buchwald Hartwig
37. Wilkinson 4 Crabtree 4 2 3 PtO gt 1 2 Stolts 3 1 Crabtree presilphiperfolan 1 ol 1 CA Ir 1 HMDS imidazole TMSCI CHzClz 2 PtO gt 5 mol EtOAc Hz 1 atm 3 TBAF THF reflux Crabtree s Catalyst 88 yield 3 steps py PtO2 5 mol 9 UI HMDS Hexamethyldisilazane 95 combined yield TMSCI Chlorotrimethylsilane Ni TBAF Tetrabutylammonium fluoride 3 9 ep presilphiperfolan 1 ol 2 presilphiperfolan 1 ol 1 Crabtree Cat 10 mol CH 2Cl2 Hz 1 atm 9296 yield No LNew 034 23201 1 5 Cyclooctadiene pyridine ticyclohexylphosphine iridium DOm9 11 000 LNew 030 23203 Hexafluorophosphate Crabtree s Catalyst 500mg 37 000 033 21711 Chlorotris triphenylphosphine rhodium I lg 15 000 039 21713 Ref Wilkinson s Catalyst 5g
38. mL 296 34591 292 34593 220g 400mL 14 38 lt 63 m SS 65 m NH2 HC M NHz HC L NHz HC 2L NH2 HC 3L NHz HC 4L 4 5nm 1 0mL 9 6 5nm 0 7mL g NH2 HC 900m2g 450m2g 1009 500g 1009 500g HN BN EL 5 pH 9 5 10 5 8 5 11 5 9 000 31 000 8 000 28 000 Wako ERPORDSE a B 1tmin 0 509 0g 0 50g 1 0g i b Presep NH HC 20 48 000 100 20 80 000 100 20 100 000 N 100 5 50 000 7 8 6 5 75 000 g 30 K TN TLC
39. ohexylcarbodiimide DCC N N Diisopropylcarbodiimide DIC N N Disuccinimidyl Carbonate DSC N Hydroxysuccinimide HOSu N PFe on NN O PN N N PFe KT N N O lt PFe 7 O N QA NZ BF4 9 LO P OEt OE NZ 259 100g 29 250 19 39 250 EE lg 59 99 259 lg g 259 g 259 100g 259 100g 500g 259 100g 500g 19 29 259 1009 5009 8 000 25 000 7 000 23 500 5 000 10 000 35 000 6 000 18 000 8 500 28 000 5 000 10 000 30 000 8 000 24 000 78 000 1 700 3 700 11 500 6 000 13 000 50 000 4 200 8 000 24 000 9 000 35 000 K OS Crabtree Wako Crabtree 1 5
40. pp iPad iPhone ijOS PC Spartan SSPD Spartan Spectra and Properties Database EDF2 6 31G DFT 25 NMR IR SMD Spartan Molecular Database 15 10 SMD 1 iSpartan iPad iPhone iTunes App Store 2 Standard 5 000 Spartan 14 Parallel Suite
41. rporate Windows 0000550 EN A ULM14 1 IN 9 105 00550 SEWS ncs 0 Stat s ene aiarentr coma Wms eyk mo 005 00580 Swerncs a ane tk 82000 005 00550 SEWS PAC1 E SDartan14 1 Year Maintenance for Education Windows 2 174 000 14 1 12 005 00550 SEWP PAC1 E SDartan14 3 Years Maintenance for Education Windows 005 00550 SEWS PACSE 14 3 SDartan14 Parallel Suite 3 Years Maintenance for Education Windows 005 00550 SE 14 3 SDartan Student Edition Single Pack Access Code Windows 01 1 SDartan Student Edition Single Pack USB Dongle Set Windows 005 00550 SXSU DW01 1 8 SDartan Student Edition 10 License Pack Windows 005 00550 SASU DWI0 10 8 SDartan Student Edition 30 License Pack Windows 005 00550 SASU DW30
Download Pdf Manuals
Related Search