The Oxo process. Ready; Catalysis Hydroformylation. Ready; Catalysis Hydroformylation

Transcription

1 eady; Catalysis ydroformylatio The xo process -developed i 1938 by tto oele -riciple method for hydroformylatio of termial alkees idustrially -more that 4 millio tos aldehyde aually -liear aldehydes more desirable Co 2 (C) 8 2 /C ( atm) o C liear (ormal) brached (iso) chemical feed stocks liear alcohols (detergets) your ame here 1/2 (C) 3 Co Co(C) 3 Δ 1/2 (C) 4 Co Co(C) 4 Stable coveiet form of Co, but iert at rt (why?) 2 σ-bod met.? 2 (C) 4 Co pka = ~1 (2), 8 (C3C) C eck ad Breslow Jacs, 1961, 4023 Sommer, Jacs, 1969, 701 (C) 3 Co regiodetermiig (C) 4 Co C (C) 3 Co (C) 3 Co 2 (C) 3 Co iso hydrogeatio eady; Catalysis ydroformylatio 1

2 eady; Catalysis ydroformylatio Asymmetric ydroformylatio: uder-developed 4 steps high yield h 2 ayashi JC, 1993, 194 h 2 (S,)-BIAS mo% h(acac)(c) 2 BIAS (4x [h]) 2/C (100 atm) C :i selectivity "beyod the discussio here" ozaki, JACS, 1997, 4413 C 3 C 3 h % ee i: 92 88:12 C 3 C C 3 4--h 4-h :13 87:13 91:9 i: 96:4 d.r. C 3 4-CF 3 -h iv :4 88:12 2 C C :11 '? C 3 3 C ()-Ambrutici Jacobse, JACS, 2001, ' * see Breit, Eur. JC, 1998, 1123, C Buchwald, JACS, 2011, eady; Catalysis ydroformylatio C succiyl chloride, 2 (±)- = C 2 A: = (resolve diastereomers) ~30% 2 00 psi 2 /C h(acac)c 2 /A (0.02 mol%) 60 o C C C 3 C C C Ac C Boc C Cbz C C 3 30:1 b:l 100% cov 89% ee TBS C 3 C 2:1 b:l 99% cov 96% ee C 3 4.8:1 b:l 100% cov 87% ee BzC C 3 C 4.4:1 b:l 99% cov 86% ee C 3 40:1 b:l 100% cov 9% ee Ac Ac C 3 C 7:1 b:l 99% cov 93% ee C 3 33:1 b:l 99% cov 99% ee C 3 1:1 b:l 99% cov 94% ee Ladis, Klosi, JACS, 200, 040 Stahl, Ladis, JACS, 2010,

3 eady; Catalysis ydroformylatio-4 dpm t-bu 0.1 mol% h(c) 2 C 11 t-bu 1 mol% ligad 2/C C 11 C Mixture of brached isomers i ligad :i h3 0.9:1 t-bu t-bu 9.2:1 Ca you explai how ad why?? va Leeuwe, ACIEE, 1999, 336 eady; Catalysis ydroformylatio Alkye hydroformylatio/silylformylatio: Usolved, but would be ice d 2 (Cy 3 ) 2 Co 2 (C) 8 Et 3, 2 /C 10 o C ole of Co is ot clear. May other metal carboyls accelerate rx. Cocatalyst could help carboyl isertio. owever, rate depedet o 2 pressure, suggestig hydrogeolysis may be rate determiig. C idai, JACS, 1997, 6448 = alkyl, 88-9% = h, 3% (much stilbee) = h, 77% (w/o Cobalt) = h,, 8%, 3:2 regio (w/o Cobalt) ' h 4 (C) 12 (1mol%) 2 hsi (1 equiv) Et 3, C (29 atm) 100 o C h 2 Si ' C CsF ' C =, r, h, cex, allyl ' =,, h, C2M2 yields mostly >70% fte poor E/Z Matsuda, JACS, 1989,

4 eady; Catalysis ydroformylatio Tadem hydroformylatio/reductive amiatio or hydroamiomethylatio [h(cod) 2 ]BF 4 (0.1mol %) 2 Xatphos (0.4 mol%) /Tol 2 C/2 (1:, 40 bar) 12 o C 2 :i 9:1-99:1 y: most >90% i lefis alkyl Amies Beller JACS, 2003, h 2 h 2 2 Xatphos ($17/g Aldrich) 2 2 =,, h eady; Catalysis ydrosilylatio ydrosilylatio What: -Si 3 catalyst Si 3 Si 3 catalyst usually = t, h, d, Ir why: Si 3 To retire rich, youg ad famous: 2 [] Si 3 = protected alcohol or or as adhesives, surfactats (major applicatios idustrially) C=C 60 -C -90 C- -100! ~ -10 kcal/mol ow: XSi 3 M Si3 X Si 3 M 2 Si 3 M 2 X Si 3 M 2 X ote i some cases X-Si bod formatio precedes -C bod formatio 4

5 eady; Catalysis ydrosilylatio hodium [h(i) - h(iii)] h(h 3 ) 3 h 2 Si 80% Si 2 h h(h 3 ) 3 Si 2 h h 2 Si 7 % h(h 3 ) 3 h 2 Si low yield h(h 3 ) 3 Si 3 h(h 3 ) 2 3 Si Si 3 h Si 3 h Chalk JMC, 1970 (21) 207 Si 3 h eady; Catalysis ydrosilylatio latium [very active, t(ii) - t(iv)] 2007:.6 metric tos of platium used for hydrosilylatio Si 2 2 t mol% 2 Si- 2 t mol% 2 Si- 2 t mol% 2 Si- 93% 98% Si 2 quat. Si 2 Si 2 as bee suggested that t colloids are the real catalyst. These are suspesios of fie particles A radius. These solutios appear homogeeous ad are able to pass through filters. B B 4% 1. ( 2 Si) 2 ; 2 t 6 2. TBAF 10 mol% MDS 2 mol% 2 t >80 %yield 87:13 B Si 2 B 8 steps Jatrophatrioe aquette, JACS, 2002, 642 Leucascadrolide A Kozmi, L, 2001, 7

6 eady; Catalysis ydrosilylatio alladium: asymmetric sythesis of 2 o alcohols also B, ir, Et mol% [d(allyl)] 2, Si 3 2. Et, Et h 2 = -alkyl yield %ee i: 60's 9-97 :1-20:1 = cex :1 ayashi, JACS, 1991, 9887 ote: they propose M accelerates.e.; Isertio is rate determiig, so get kietic product ote: w/ BIA (ad other chelatig phosphies) o reactio, propose iert 16e s.p. complex: but: (best substrate) h h 2 Si-Si 3 d(bia) 2 d Si 3 vs. h d Si 3 1. Li, I 2. BF Sih 2 Si 3 4%, 8% ee 70% ayashi, Ito Tetrahedro, 1994, 33 h 0.mol% [d(allyl)] 2, Si 3 Si 3 h h 9-97% ee e poor or eutral aromatic Johase JACS, 2002, 48 eady; Catalysis ydrosilylatio Cu: a alterative to cojugate add. for early work with [(h 3 )Cu] 6 'strykers reaget' see stryker, jacs, 1989, 8818 MgBr; Et MS = polymethylhydrosiloxae cheap, safe Dyamic kietic resolutio Cu[(tol)-BIA] ( mol%) atbu ( mol%), MS (1.0 equiv) glovebox Si mw = Cu[(tol)-BIA] (10 mol%) atbu (1.7 equiv), MS (2.2 equiv) 2. TBAF Si 3 TBAF -alkyl 1 y ~80 ee ir Bu (C 2 ) 2 h ' ' i-r B Buchwald Jacs, 2000, 6797; 2002, 2892 h 91% ee 91:9 cis:tras 89% yield h 93% ee 93:7 cis:tras 94% yield i-r 93% ee 92:8 cis:tras 9% yield h 91% ee 97:3 cis:tras 90% yield 6

7 Cu-Catalyzed ydrosilylatio: chaism ad Applicatio tbusi 3 Si 3 L Cu KtBu L Cu tbu Si 3 (formed i situ from iodide) Et 2 C Mg (±)- CuL Si 3 L Cu tbu Si 3 -BIE, atbu (1.2 equiv) MS, tbu >8%, 93%ee CuL L Cu C 3 amds, I Buchwald, ACIE, 200, 6177 eady; Catalysis ydrosilylatio 7

8 eady; Catalysis ydrosilylatio eady; Catalysis ydrosilylatio Ketoe ydrosilylatio: a remarkable catalyst some substrates [CpW(C) 2 Is] [B(C 6 F ) 4 ] mol%, Si 2 h Si 2 h y ~90 -catalyst soluble i "a few molecules of substrate per molecule of catalyst" -catalyst precipitates at ed of reactio; decat product -ca recycle catalyst: cycle 1 TF (iitial) Is Dloumaev ad Bullock (Brookhave atioal Laboratory) ature, 424, 2003, 30 8

9 eady; Catalysis ydrosilylatio Eatioselective ketoe hydrosilylatio Sih 2 2 h 3 L* AgBF4; 3 9% ee 99% ee 80% ee L = ishiyama Tet: asym, 1993, 143 "ybox" ote: M AgBF4 or AgSbF6 AgBF4 $72/10g AgSbF6 $42/g (aldrich) [M][BF4] or [M][SbF6] Ag I geeral, hydrogeatio works better tha hydrosilylatio -usually see silae that does T give useful protectig group -ofte used as 'bechmark' reactio for ew ligads -compare 2-100% atom effeciet; Sih 2-0.% atom effeciet eady; Catalysis ydrosilylatio ad ow for somethig differet... ow to do reductios with a oxidat Usual hydrosilylatio requires.a. to Si-: Si M Si M 2 Toste et. al. disovered [22] with metal oxo Si 3 I h igh valet metal oxo usually 3 strog oxidizig... e h Si 3 3 h 3 h 3 Toste, JACS, 2003, 406 e I Si3 h 3 e I Si3 h 3... but here it's promotig a reductio Alterative mech: Abu-mar JACS, 200,

10 eady; Catalysis ydrosilylatio Eatioselective imie hydrosilylatio C S 2 e h 3 C = 4- t Bu-h 1 e h 3 ()h 2 1 (3 mol%) h 2 Si ()h 2 Ar Ar ()h 2 ()h 2 ()h 2 C 3 ()h 2 h X >98% ee X =,, CF 3, I Ts >99% ee C 3 = 1,3; 9-96% ee C 3 C 3 99% ee Toste, JACS, 200, eady; Catalysis ydrosilylatio alkee silylformylatio but Sih 2 Si(ir) 2 1 mol% h(acac)(c) psi C as above Si(ir) 2 Sih 2 C h C ote Si-C formatio preceeds -C formatio Sih :1 allyl 64 4:1 ir 79 6:1 % yield cis/tras C 3 Tadem silylformylatio/allylatio allylic alcohol; ca repeat process i-r Si h(acac)(c) 2 (1mol%) 1000 psi C i-r Si i-r Si 2 2 i-r 9% yield 77:23 sy,sy:rest i-r Si h(acac)(c) 2 (1mol%) 1000 psi C i-r Si 1.TBAF 2. Ac 2 i-r Ac Ac 70% yield 23:1 1, ati:1: sy Leighto JACS, 1997; 12416, 2000, 887; 2001,

11 The image caot be displayed. Your computer may ot have eough memory to ope the image, or the image may have bee corrupted. estart your computer, ad the ope the file agai. If the red x still appears, you may have to delete the image ad the isert it agai. eady; Catalysis ydrosilylatio Aldehyde Silylformylatio 3 C Si 2 h 0. mol% [(CD)h] 2 hsi() 2, C Si 2 h Ac 2 60% 80% 70% Si 2 h Si 2 h roposed: Si 2 h Lh Si 3 L L h Si 3 L h L 3 Si C L L h Si 3 Wright, JACS, 1993,

12 eady; Catalysis ydrozircoatio ydrozircoatio Schwartz's reaget 2 o alkyl zircoium complexes isomerize to 1 o alkyl zircoium species via β-hydride elimiatio/isertio sequece. Ultimate formatio of strogest -C bod Cp Cp Cp Cp ot favored: (IV) (d0) ca't backbod slight excess (usually 1.1 equiv) Schwartz JACS, 1974, , 679; With 1 equiv with 1.1 equiv 16 2 : eady; Catalysis ydrozircoatio Electrophilic Fuctioalizatio Br 2 or BS Br Br Ac 2 2, a C isertio, fuctioalizatio C (1.atm) Br Br 2 / BF 3 Et 2 eactios are stereospecific: Maitai olefi geometry or stereochemistry Schwartz JACS, 197, 228; ACIEE 1976, 333 eview: Labiger, Com. rg Sy vol 8, 667 Trasmetallatio (most commo applicatio. Great way to make viyl orgaometallics) L M-X stereospecific M X M = Al, B, Cu, g, i, d, S, Z Wipf, tetrahedro, 1996,

13 eady; Catalysis ydrozircoatio TIS 1. Cp 2 () (3eqiv) 2. BS TIS Br 1. tbuli 2. MgBr 2 3. C TIS itermediate i sythesis of FK06. Schreiber jacs, 1990, 83 I 1. Cp 2 () 2. Z 2 Z I 3 Si survived 3 Si d(h 3 ) 3 6. mol% 1. Cp 2 () 2. I 2 3. steps I 3 Free K 3 reduced by I 3 3 Si Itermediate i sy of F Jacobse, JACS, eady; Catalysis ydrozircoatio ' ()Cp 2 o added ligad Br β-, but o elimiatio ()Cp 2 d(ac) 2 LiBr ' Fu, JACS, 2004, 82 Et 99% h Et 99% TBDS B 73% T C 3 68% h 77% h Et Et 8% Et 13

14 eady; Catalysis ydroacylatio ydroacylatio Desired eactio/obstacle: M M icreased C pressure would decrease decarboylatio but would also retard C isertio ' (h 3 ) 3 h ( mol%) 10 o C, 24 h (20 mol %) 49-92%y ' 13 egs =, Alkyl ' = aryl, alkyl 2-2 h pyridie recruits aldimie to h; accelerates C activatio - 2h 2 ' 2 ' h h Ju JC, 1997, 1200 with alkyes: ACIEE, 2002, 2146 eady; Catalysis ydroacylatio Itramolecular hydroacylatio 20 mol% [h(dppe)][ 4 ], ethylee, 6 o C hl hl 2 6% cis: 63% tras: 6% 8% Shair, JACS, 2000, [h(dppe][bf 4 ]?? h h = -ex 7% = h 88% Fu, JACS, 2001,

15 eady; Catalysis -X Additios to lefis 1