Synthetic Methodology. Using Tertiary Phosphines. as Nucleophilic Catalysts
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1 Synthetic Methodology Using Tertiary osphines as Nucleophilic Catalysts u 2 (P 3 ) D. Ma, X. Lu Pd 2 (dba) 3.CCl 3 /P 3 /Ac or Pd(Ac) 2 /P B. M. Trost u 2 (P 3 ) Y. Inoue 1988
2 Cat. (1 mol%) benzene, 60 o C Cat. T (h) Yield (%) Ir 5 (I-Pr 3 P) e 7 (i-pr 3 P) u 2 (n-bu 3 P) u 2 () u 4 () ucl 2 () h() hcl() [Ir(cod)Cl] ucl hcl Ir 5 (i-pr 3 P) 2, benzene 35 o C, 24 h /Cat Yield (%) n-bu 3 P 2 28,, 4 48,, 6 73,, 8 99,, i-pr 3 P ,, 8 30
3 1 C 2 3 A 1 C M 1 C 2 M A 1 C M 2 3 -M 1 C C 2 M 3 1 C M 3 2 Me Pd 2 (dba). 3 CCl 3 (5 mol%) i-pr 3 P (10 mol%) C 3, reflux, 30 h Me = n-c % = n-c % = n-c % = n-c %
4 1 2 Cat.? 1 2 ()- 2 = alkyl, t Pd(Ac) 2 (2.5 mol%) P 3 (35 mol%) toluene, reflux 31 h 31% t
5 t cat. benzene reflux h t t cat. (2.5 mol%) P 3 (mol%) Pd(dba) % 31% 55 54% 19% % 0% Pd(Ac) % 16% 55 52% 11% % 0% t 1 2 (100 mol%) benzene, rt, 8 h (100 mol%) benzene, rt, 8 h t = C % = n-c % = n-c = n-c % 1 = n-c = C %
6 C 2 Cl C 3 C 2 Cl C 2 2 C P
7 (100 mol%) t (100 mol%) benzene, reflux t t (100 mol%) t (100 mol%) benzene reflux, 35 h 72% (10 mol%)-t (10 mol%)/80 o C 79% 3P (100 mol%)-t (100 mol%)/rt 81% (10 mol%)-t (10 mol%)/rt 81%
8 3 5 benzene (100 mol%)/80 o C 79% (100 mol%)/rt 84% (10 mol%)/rt 80% (5 mol%)/rt 65% (10 mol%) benzene, rt 34 h, 76% aq. K 2 C 3 (10 mol%) benzene, rt 34 h, 81% (10 mol%) benzene, rt h, 80%
9 /rt 75-89% 1 : C 2 1 C 2 3P 1 1 3P C 2 3P C 2 transfer transfer 1 1 C 2 C 2 3P 1. C 2 3P 1 1 transfer C 2 C 2 C 2 C 2 C
10 Tertiary phosphine catalyzed reactions: 2 C 2 1 Isomerization [Trost; Lu] C 2 1 or C 2 1 C P three carbon synthon Nu - Nu [Trost; Lu] C 2 1 Umpolung addition C 2 1 [32] Cycloaddition [Lu] 1,3-Dipole or A
11 Isomerization 1 shift 1 lectron-rich lectron-deficient C C C WG Nucleophilic addition lectrophilic addition WG path a: Michael addition path b: Umpolung addition Nu WG Nu (β-addition) γ α β WG (γ-addition)
12 Umpolung addition: α-addition 1 Nu 1 =,, 3 C- γ-addition Nu 1 C 2 C 3 2 C 2 C 3 1 C 2 C C 2 C 2 C C 2 C 3 C 2 C 3 2 C 2
13 Cycloaddition A C C 2 or C 2 C 2 C 2 C 2 Me Y N 3 P C 1 benzene 2 Me rt Y : Ts, SS (Me 3 SiC 2 C 2 S 2 -) Y N 1 C 2 Me yield: >90% Ts N 1 C 2 Me. C 2 Me Ts N 1 C 2 Me C 2 Me P 3 A Ts N Ts N 1 Ts N 1 1 C 2 Me C 2 Me P 3 B
14 Important step for regenerating : C 2 C 2 C 2 An electron-withdrawing group is necessary! Tandem eactions To Construct eterocycles
15 γ addition Nu 1 Nu 2 Nu 1 Nu 2 or C C C C Nu 1 Nu 2 α addition C Nu 2 Nu 1 Nu 2 Nu 1 umpolung addition C conjugate addition C Tandem eaction of γ-addition and Intramolecular Michael Addition Carbon-oxygen dinucleophiles 1. or 2 2 P 3 γ-addtion intramolecular 1 Michael addition 2 t C C C From: t
16 1 1 active methylene compound. P 3 (5 mol%) C Me C C cyclized product γ-adduct Active Methylene compound t/t Cyclized Product,% γ-adduct % t t Bu Me MeC /24 h 110/24 h 70/2 h 70/5 h 70/5 h t Me MeC /5 h 70/5 h 70/5 h 70/5 h t Me 70/5 h active methylene compound P 3 (40 mol%) 110 o C Me C C cyclized product γ adduct Active Methylene compound T (h) Cyclized prodoouct γ-adduct Me t Bu Bn n Pr i Pr
17 P 3. 2 P 3 P P 3 2 P P P P 3 2 P Nitrogen-nitrogen dinucleophile Nitrogen-oxygen dinucleophile TsN NTs TsN NTs 2 2 = CMe 93% C 81% CCy 96% TsN 2 P 3 TsN 2 2 = CMe 66% CCy 66%
18 Nu 1 Nu 2 Nu 1 Nu 2 Nu 1 Nu 2 or Nu 1 Nu 2 Nu 1 Nu 2 Nu1 Nu 2 Tandem eaction of α-addition and Intramolecular Michael Addition TsN NTs 2 P 3 TsN NTs 2 2 = C 2 t, 86% Cn-Pr, 83% TsN NTs TsN NTs 2 = C 2 t, 88% 2
19 Nu 2 Nu 1 Nu 2 Nu 1 Nu 2 Nu 1 Nu 1 Nu 2 Nu 2 Nu 1 Nu 1 Nu 2 ighly egioselective Construction of Spirocycles
20 C 2 t A C 2 t B C 2 t 3 P Time (h) Yield (%) A : B C 2 C 3 3 P : 20 C 2 C 3 Bu 3 P : 15 C 2 C P : 25 C 2 C 2 5 Bu 3 P : 25 CC 3 3 P : 37 3 P : 17 S 2 3 P : 0 C 2 t C 2 t C 2 t (1.0 mmol) (2.0 mmol) A C 2 t B C 2 t C 2 t rt, benzene No reaction 135 o C, xylene Trace (with polymerization of acrylate) Bu 3 P (10 mol %) rt, benzene, N 2, 12h 85% (A : B = 89 : 11)
21 . C 2 1 C 2 1 C 2 1 P 3 C 2 1 C 2 1 C 2 1 transfer P 3 C 2 1 C 2 1 C 2 1 C 2 1 C 2 1 Ct P 3 (10mol%) benzene or toluene eflux A Ct Ct B Substrate yield,% A/B Substrate yield,% A/B 73 58/42 N =Boc,33 Ts 94 Bn n. r. 62/38 82/ Cl 100 Br 98 Me 92 = 99 Me 55 73/27 84/18 82/18 78/22 83/17 79/21 83/17 BnN N Bn NBn No reaction /20 65/35
22 Ct P 3 Ct tc P 3 P 3 Ct Ct Ct B A CBu t P 3 (10mol%) benzene or toluene eflux A CBu t CBu t B Substrate yield,% A/B Substrate yield,% A/B 63 78/22 N =Boc, 92 Ts 93 92/8 91/ Br 98 Me 96 = 98 Me 95 80/20 95/5 93/7 92/8 91/9 92/8 BnN N Bn NBn No reaction /14 74/26
23 CBu t Bu 3 P (10mol%) benzene or toluene eflux A CBu t CBu t B Substrate yield,% A/B Substrate yield,% A/B 19 89/11 N =Boc, 96 Ts 30 Bn n.r. 100/0 100/ poly. Cl poly. Br poly. Me 10 = poly. Me 96 92/8 100/0 90/10 N Bn BnN NBn No reaction /5 100/0 Synthesis of (-)-inesol cis-spirovetivanes (-)-hinesol 1 etrosynthetic analysis: 10 2 C cis-spirovetivanes
24 or P 3 P 3 = C t Bu = Bu or = C t Bu favored disfavored disfavored disfavored P 3 P 3 P 3 P 3 -P 3 -P -P 3 -P 3 3 A B C D From allenoate/: 23%, A/B/C/D=73/12/12/3. From allenoate/bu 3 P: 41%, A/B/C/D=83/10/7/3. From butynoate/bu 3 P: 63%, A/B/C/D=94/6/0/0. A was confirmed by X-ray crystallography. [32] 1) 2, Pd-C, t C t Bu 2) Me, reflux 83% CMe Zn-C 2 I 2 -TiCl 4 C 2 Ts C 3 C 2 Cl 2 -TF 82% CMe Benzene, reflux 90% CMe MeMgI t 2, 69% C 3 ()-hinesol
25 PCC C 2 Cl 2 C 3 N 2 N benzene reflux (C 3 ) 2 CuLi. LiBr TF, -90 o C-0 o C N 2 N 2 N 4 Cl mcpba C 2 Cl 2, rt N C 3, rt Me N 2 t 3 N C 3 2 CuLi. LiBr -78 o C N Me N 2 (S) C t 2 Bu toluene, rt 95%ee C 2 t Bu (-)-hinesol 94%ee 94%ee A Catalytic eaction of Carbon-osphorus Ylide
26 Two Types of eactions of Allylic osphorus Ylides with lectron-deficient Alkenes: Intramolecular Wittig reaction A 2 P3 2 P3 3 3 Intramolecular nucleophilic substitution P 3 -P 3 Both reactions are stoichiometric with regard to phosphines.
27 Important step for regenerating : C 2 C 2 C 2 An electron-withdrawing group is necessary! 1 P 3 A B B allylic ylide
28 1 1 base 1 Br Br B Ac 1 1 base 1 Ac B Boc C 2 t-bu B t-bu 7 - B 7 -
29 Stoichiometric reaction: Br K 2 C 3 (1.5 eq.) N toluene, 90 o C 74% (1 eq.) (1 eq.) Catalytic reacton: N P 3 = C 2 t Br (1.2 eq.) N (1 eq.) P 3 (10 mol %) K 2 C 3 (1.5 eq.) toluene, 90 o C 88% N = C 2 t A First Catalytic Ylide eaction (32 Addition): C-3 C-2 catalyst [32] product 1 N 1 N Br yield, (%) 1 =, 88 n-pr, 60, 50 p-mec 6 4, 66 p-mec p-n 2 C 6 4, 71
30 C-3 C-2 catalyst [32] product yield (%) Br Br C C 2 t C 2 t C 2 t t 2 C C t 2 C C 2 t (10 : 1) C 2 t C 2 t p-n 2 C 6 4 Br C 2 t C 2 t t 2 C C 2 t p-n 2 C C-3 C-2 catalyst [32] product yield (%) Br X X X = 72 X = Me 65
31 C-3 C-2 catalyst [32] product yield (%) Ac 1 N 1 N =C 2 t 1 = 76 1 = 62 =C 1 = 64 Boc =C 2 t 74 Asymmetric Version
32 Boc C 2 t Nt (,)-Me-DuPS rt, 10 h Toluene t 2 C Yield Nt ee % n-pr i-pr i-bu 2-Furanyl p-nitrophenyl 2,3-Dichlorophenyl P P (,)-Me-DuPS Activation of Aliphatic C- Bonds
33 C 2 t P 3 toluene, rt. NC t 2 C 89% C P 3 C 2 t MS, toluene, reflux NC t 2 C 86% NC Br, K 2 C 3 toluene A X = C 2 t B
34
35 反应可能的机理 : Boc NC C 3 NC _ C 2 NC t-bu t-bu C 3 NC C 2 NC A Boc _ C 2 t-bu B B M N M P P N P P 3 2 1
36 C 2 t P 3? C 2 t NC
37 . C 2 1 NC Ar 2 P 3 ( 10 mol% ) xylene, reflux NC Ar 2 C 2 1 entry Ar ab 2 ab 3 abd 4 ab 5 ab 6 ab 7 ac 8 ac 9 ac 10 ac 11 ac p-mec 6 4 p-n 2 C 6 4 p-brc 6 4 p-clc 6 4 p-c 3 C 6 4 t t t t t t t t t t tbu C 3 t ipr C 3 yield a. 氩气下,P 3 (10 mol%) 在二甲苯中回流, 经 3 小时向其中滴加底物的二甲苯 (0.2 M) 溶液. b. 完成滴加后反应 0.5 小时. c. 完成滴加后反应 20 小时. d. 未检测到产物. NC C 2 t Base C 2 t P 3 C 2 t P 3 C 2 t P 3 C 2 t P 3 C 2 t
38 NC Boc C 2 t NC C 3 t 2 P Toluene rt C 2 t C 2 t Boc NC C 3 NC _ C 2 NC t-bu t-bu C 3 NC C 2 NC A Different eactivity of Amine and osphine Nucleophilic Catalysts osphine-catalyzed Pathway Amine-Catalyzed Pathway t Quinuclidine C 3 C 2 t t regio isomers
39 osphine-catalyzed Pathway t t t Amine-Catalyzed Pathway t Quinuclidine C 3 P 3 P 3 N 3 Cycloaddition 1,4-addition C 2 t P 3 t N 3 1,2-Proton shift limination of C 2 t Proton transfer limination of 3 N t C. A. vans, S. J. Miller, J. Am. Chem. Soc. 2003, 125, A 1,3-dipole 1 1 shift isomerization 1 Nu 1 =,, C 3 α-addition Nu γ-addition 1 1 cycloaddition allylic ylide B
40 Advantages of the reaction: Catalytic to the phosphine used. Atom economy. Acknowledgements Cheng Guo Zhenrong Xu Cheng Lu Chunming Zhang Yishu Du Jianqing Feng Chinese Academy of Sciences National Natural Science of China The Major State Basic esearch Program
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