Chem 634. Metal Mediated Substitution Chemistry. Reading: Heg Ch 1 2 (handout), CS-B 7.1, , 11.3, Grossman Ch 6
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1 Chem 634 tal diated Substitution Chemistry eading: Heg Ch 1 2 (handout), CS-B 7.1, , 11.3, Grossman Ch 6
2 Announcements Problem Set 1 due NW. Mary Beth Kramer Lectureship 101 Brown Laboratory September 25, 2015, 4pm Weaving Faculty Professional Development with Learning Space Affordances Gabriela Weaver Ph.D. University of Massachusetts Amherst Department of Chemistry Many institutions are making significant investments in learning spaces that will allow for innovative, student-centered and collaborative forms of teaching and learning. These approaches to teaching are supported by a broad body of literature. However, few current faculty were taught in environments like this themselves or have experience teaching in them. Faculty professional development through institutional units/ centers exists in some form at most institutions. Traditional faculty development has been optimized for improving lecture-based teaching practices. As calls for reform in STEM education begin to coalesce around active-learning approaches, then, it is necessary for faculty development to also shift its focus. UMass has been in the process of providing faculty with professional development opportunities tailored to our team-based learning classrooms for the last 3 years. As faculty access to those spaces has expanded, our curriculum has responded to the needs of an audience interested in a broader view of active-learning. In this presentation, I will describe our evolving professional development approach tailored to active learning, faculty use of our active learning facilities, and current thinking on course and space design that undergirds our work. This is part of a larger multi-institution project through the Bay View Alliance in which we are exploring the overarching question of how PD-influenced instructional practices combine with learning space affordances to affect the learning experience of students. weaver.html
3 Copper Promoted Substitution Chemistry S N 2 type eactions: Br H Ph 2 CuLi S N 2 reaction 1 >2 >>3 Tf~Ts~I>Br>Cl H Ph chanism not clear eview: Comp. rg Synth, Vol 3, Section 1.5
4 Copper Promoted Substitution Chemistry Also sp 2 systems: Tf Bu H 2 CuLi Bu Bu H Bu + 10% E-isomer Also works with But not used very often now...see later TL, 1980, 21, 4313
5 Copper Promoted S N 2' Chemistry isotopic label D BuMgBr Cat. Cu D Bu + Bu D w/ 10% CuCl: 39% 61% w/ 10% CuCN: 0% 100% However, with PhMgBr + CuCN: General S N 2' mechanism: D + Ph Ph D 51 53% 47 49% Nuc LG Nuc Goering, JC, 1986, 51, 2884
6 eactions With Acid Chlorides ecall: 'Li or 'Mg H Cl ' ' ' cannot stop here, ketone more reactive However: ' 2 CuLi Li Cl ' clean
7 Palladium (and Nickel) Catalyzed Cross Coupling + M ' L n Pd(0) cat. ' aryl or vinyl C-C bond : Tf>I>Br>Ts~Cl M= -Sn 3 (Stille reaction) -B() 2 or B(H) 2 w/ base (Suzuki reaction)* -Si 3 (Hiyama reaction) -Mg (Kumada-Curriu reaction) -ZnBr (Negishi reaction)* * = 2010 Nobel Prize
8 Basic chanism ' L n Pd(0) reductive elimination oxidative addition L n Pd II L n Pd II M ' transmetalllation M
9 Palladium and Nickel Sources Palladium (0) Sources Palladium (II) Sources (educed In Situ) Pd(Ac) 2 Pd 2 (dba) 3 dba: Pd(Cl) 2 Ph Ph (CN) 2 PdCl 2 Pd(PPh 3 ) 4 Note: dba and PPh 3 are ligands. Pd Cl 2 Nickel Sources Ni(CD) 2 Ni 2 (=Cl, Br, I) 1,5-CD:
10 Ligands = Tf, I, Sometimes Br (easy oxidative addition) PPh 3 Ph 2 P dppe PPh 2 Fe PPh 2 PPh 2 dppf = Br P(o-tol) 3 PPh 2 PPh 2 ' = Cl Pt-Bu 3, PCy 3, NHC's P' 2 '=Cy, t-bu Ligand is the most important part of the catalyst for controlling reactivity.
11 Active Catalysts for xidative Addition 18 e- 16 e- 14 e- 12 e- Pd(P 3 ) 4 Pd(P 3 ) 3 Pd(P 3 ) 2 Pd(P 3 ) 1 -P 3 -P 3 -P 3 (with PPh 3 ) (P 3 ) 2 Pd Larger more electron-rich ligands favor lower coordination numbers required for Cl Note: the need for low valent Pd(0) explains why Pd 2 (dba) 3 and Pd(PPh 3 ) 4 can be problematic. Also, this trend explains why metal:ligand ratio can be very important to reactivity.
12 Sonogashira eaction Pd(0) cat CuI cat Et 3 N
13 Formation of Copper Acetylide pka ~ 20 H CuI I Cu(I) H I Cu(III) H NEt 3 pka' ~ 9 Cu
14 chanism L n Pd(0) reductive elimination oxidative addition L n Pd II L n Pd II transmetalllation Cu Cu H NEt 3 HNEt 3
15 Hartwig-Buchwald Enolate ylation Pd(0) cat NatBu ' ' ' L n Pd(0) L n Pd II ' C 2 L n Pd II Na ' Na tbuna ' H
16 Buchwald-Hartwig Amination HN 2 L n Pd(0), base N 2 =Br, Cl, Tf Similar cross couplings with H, F-, etc. These are challenging due to E. Buchwald: ACIE, 2008, 47, 6338 Hartwig: Acc. Chem. es., 2008, 41, 1534
17 Buchwald-Hartwig Amination HN 2 L n Pd(0), base N 2 =Br, Cl, Tf Consider pk a s: typical bases: K 3 P 4 or tbuna pka': 8 17 vs. HN 2 pka: 35
18 Buchwald-Hartwig Amination eductive Elimination Difficult Typical Ligands: N 2 L n Pd(0) L 1 Pd II N 2 BH L 1 Pd II LnPd II ipr -Phos PCy 2 ipr ipr PtBu 2 ipr tbu--phos B H N 3 NH + like (pka ~ 9) ipr PCy 2 ipr BrettPhos
19 Heck eaction L n Pd(0), base (or ) Alkenes as nucleophiles. Achieves the arylation or vinylation of an alkene. Historically, the Heck eaction preceded all other palladium-catalyzed cross-couplings Nobel Prize Also called the Mizoroki Heck reaction. Mizoroki published similar findings just prior to Heck s work.
20 chanism Base H L n Pd(0) oxidative addition Base H L L n Pd II n Pd II β-hydride elim. H L n Pd II L n Pd II migratory insertion alkene binding
21 Notes on the Heck eaction Intermolecular (alkene and halide on different molecules): Somewhat limited scope. Normally limited to CH 2 CH 2, mono- and di-substituted alkenes. Tri- and tetra-sub. alkenes are too poor of ligands to engage Pd(II) intermediate. Electron-rich alkenes generally better than electron-poor. egioselectivity is often poor. Intramolecular (alkene and halide tethered together): Much better scope. Can form carbocycles and heterocycles of all types. Mono-, di-, tri- and tetra-substituted, electron-rich and electronpoor alkenes all work.
22 Example of Intramolecular Heck eaction Pd(Ac) 2 cat. PPh 3, Et 3 N N N I
23 Stereospecificity ' H Pd II H cis-migratory insertion H ' Pd II H ' cis-β-hydride elimination H ' H NT ' Pd II H H
24 Exo Cyclization Preferred N I Pd(Ac) 2 cat. PPh 3, Et 3 N N N exo-cyclization PEFEED endo-cyclization NT exo strongly preferred 5-exo, 6-exo very easy to accomplish difficult to form small rings (3-exo, 4-exo, etc) Via: N or H Pd II N H Pd II
25 Asymmetric Intramolecular Heck eaction I N Si 3 Pd(Ac) 2 (S)-Binap Si 3 N 84% yield 95% ee (97.5:2.5) Binap: PPh 2 PPh 2 Chiral Can be resolved verman, JACS, 1998, 120, 6500 Shibisaki has also contributed to this area
26 Heck Carbonylation C, Nuc L n Pd(0), base Nuc = I, Tf L= PPh 3, etc = Br L = antphos = Cl L = PCy 2 PCy 2 Nuc = H 2 H H 2 N HN 2 Bu 3 SnH Product = H NH N 2 H
27 chanism L n Pd(0) Nuc L n Pd II Nuc L n Pd II C L n Pd II C
28 eductive Elimination Details Transmetallation: L n Pd II Nuc-H transmetallation or salt metathesis L n Pd II Nuc.E. Nuc r: Addition-Elimination: L n Pd II Nuc-H base L n Pd Nuc Nuc Both mechanisms are known.
29 Cross Coupling With Alkyl Groups Dec Br + 9-BBN hex Pd(Ac) 2 (cat) PCy 3 (cat) Dec 85% hex + 2% hex 9-BBN: B Limited to 1 electrophiles with Pd. Fu, JACS, 2001, 123, Fu, ACIE, 2002, 41, 945 (Cl, Ts)
30 2 Alkyl Halides Br + BrZn ' NiBr 2 diglyme (S)-pybox ' Fu, JACS, 2003, 125, Cl racemic! Br + BrZn ' NiBr 2 diglyme (S)-pybox Cl 82%, 91% ee ' Fu, JACS, 2005, 127, (S)-pybox: N N N i-pr i-pr
31 Iron Catalysis Cl + HexMgBr Fe(acac) 3 Hex MgBr + FeCl 3 Br tmeda, -78 C + less than 20% Furstner, ACIE, 2002, 3856 (Fe 2- ) Nakamura, JACS, 2004, 126, 3686 Furstner, Acc. Chem. es., 2008, 41, 1500
32 Ullman/Goldberg Coupling H N N N N =I,Br CuI (cat) Ligand (cat): Ligands HN NH N N, etc Good for weakly basic N-nuc (amide, heterocyclic, etc.) Limited to I and some Br. Buchwald Chem. Sci. 2010, 1, 13.
33 π-allyl Chemistry Tsuji-Trost L n Pd(0) PdL n η 1 Pd η 3 = Cl, Br, Ac, C(), P() 2, etc
34 π-allyl Chemistry Ac L n Pd II L n Pd II D Backside attack D D
35 π-allyl Chemistry π-allyl fragments can racemize: Cl L n Pd(0) Pd II L n Pd II L n L n Pd II Pd II L n Pd II L n achiral If the metal π-allyl can isomerize to the terminal position, this provides a pathway for racemization. PdII L n L n Pd II L n Pd(0) D slow D + Pd(0)
36 Substitution eaction with π-allyl Electrophiles Type 1: Non-basic Nucleophiles (pka < 25, DMS) Cl L n Pd(0) Pd II L n nuc nuc note: less sub. side of π-allyl Na nuc = amines Ph - double backside displacement = net retention N 2 etc.
37 Substitution eaction with π-allyl Electrophiles Type 2: Transmetallation Cl L n Pd(0) Pd II L n Bu 3 SnPh L n Pd II Ph Ph transmetallation occurs with: 3 Sn, B(H) 2, etc. Net inversion observed
38 Asymmetric Variant NH HN PPh 2 Ph 2 P Trost modular Ligand: "TML" Bz Bz + meso Ph 2 S N 2 (allyl)pdcl 2, L* Bz = L*Pd Bz 2 N Ph 2 S >90% ee Bz Trost: Chem. ev., 2003, 103, 2921 Acc. Chem. es. 2006, 39, 747 Lloyd-Jones, JACS, 2009, 131, 9945 stereoselectivity in AAA reaction
39 ther tal π-allyl Chemistry Mo π-allyl Ph D Ac Mo(C) 4, L* H (C) 4 L*Mo D Ph H -ray and NM Na Ph D H Double etention at more hindered side Trost, JACS, 1987, 109, 1469 Lloyd-Jones, JACS, 2004, 126, 702
40 ther tal π-allyl Chemistry Mo π-allyl Ac Na Mo(C) 3 (tol), L* Br Br 95%, 94% ee L*: NH HN N N THC H Trost, L, 2007, 9, 861
41 hodium and Iridium π-allyl Chemistry t-bu H [Ir(cod)Cl] 2, L* 87%, 95% ee L* P Ph N Ph Hartwig, JACS, 2003, 125, 3426
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