Synthesis of 1,3-Diols via Controlled, Radical-Mediated C-H Functionalization
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1 Synthesis of 1,3-Diols via Controlled, Radical-Mediated C- Functionalization Chen, K.; Richter, J. M.; Baran, P. S. J. Amer. Chem. Soc. 2008, 130, Literature Group Presentation Wynter Gilson August 1, 2008
2 Introduction Previous work on 1,3-diol synthesis. 1,3-diol synthesis inspired by LF rxn. Challenges of this method. Use of this method towards synthesis of natural compounds. Comparison of selectivity of C- bond activation with other methods.
3 Previous work on 1,3-diol synthesis Me Conjugate addition (reduction) Aldol (reduction) Allylic hydration Direct oxidation or
4 Inspiration from the ofmann- LÖffler-Freytag (LF) reaction General LF reaction X 1) acid 2) radical initiator X Base R2 = alkyl, aryl, = alkyl, acyl, X = Cl,, I *Reaction is 99 years old. *Considered one of the first directed C- activation reactions ever reported. Kurti, L.; Czako, B., Strategic Applications of amed Reactions in rganic Synthesis; Elsevier Academic Press: Burlington, MA, 2005; p 208.
5 Incorporating LF rxn into 1,3-diol synthesis Modified LF reaction R 1. LF Reaction 2. ydrolysis A F R E R a B R 2 b R C R D
6 Incorporating LF rxn into 1,3-diol synthesis Modified LF reaction R 1. LF Reaction 2. ydrolysis A F R E R a B R 2 b R C R D
7 First Challenge R a B b R C * Most -bromocarbamates gave < 30 % conversion * Trifluoroethyl carbamate gave more reactive -centered radical
8 Generate more reactive radical via trifluoroacetylisoleucine methyl ester anched Carbon Chain Target Site 2 Two Sterocenters C 2 Me CCl 4, 23 C 1h, dark C 2 Me light 23 C C 2 C 2 Me a) Reddy, L. R.; Reddy, B. V. S.; Corey, E. J. rg. Lett. 2006, 8, b) Duhamel, L.; Ple, G.; Angibaud, P. ; Desmurs, J. R. Synth. Commun. 1993, 23, c) Beebe, R.R.; Wolfe, J. W.; J. rg. Chem., 1970, 35,
9 Variation of trifluoro-acetyl moiety C 2 Me i-pr 2 Et TF 23 C C 2 C 2 Me 1. ascme TF 2. K 2 C 3, Me, 0 C SC 2 C 2 Me C 2 Me ai Me 2 C Ag 3, 1:1 TF C, 91% C 2 Me IC 2 C 2 Reddy, L. R.; Reddy, B. V. S.; Corey, E. J. rg. Lett. 2006, 8,
10 Applying trifluoro compounds to 1,3-diol synthesis C 2 C CF 3 C 3 C 2 CF 3 97 % CF 3 PhCF 3, C 4 hv, 100 W flood lamp
11 Second Challenge Modified LF reaction R 1. LF Reaction 2. ydrolysis A F R E R a B R 2 b R C R D
12 Second Challenge Modified LF reaction R 1. LF Reaction 2. ydrolysis A F R E R a B R 2 b R C R D
13 Second Challenge Aliphatic Cases: CF 3 Ag 2 C 3 CF 3 Ac K 2 C 3 (69 % isolated overall) Benzylic Cases: Ph Ph ame Ph Ph (91 % isolated, dr 1:1)
14 Synthesis of 1,3-diol C 2 C CF 3 C 3 C 2 CF 3 97 % PhCF 3, C 4 hv, 100 W flood lamp K 2 C 3 Ag 2 C 3 CF 3 then Ac (69 % isolated overall)
15 Scope of 1,3-diol synthesis
16 Synthesis of natural products Previous synthesis: 4 steps, 12% 70 %, dr 8:1 42 % 9 Previous synthesis 36 % dr 3:2 α = isorengyol β = rengyol Previous synthesis: 13 steps, 29 % 8 steps, 3.2%, dr 3:1
17 Comparison of selectivity of tertiary C- bond activation Gives both alchohol and ketone products. Curci [] (dioxirane) (SbF 6 ) 2 Targets remote tertiary position Fe CC 3 CC# X White Fe-based catalyst X a) Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J. Amer. Chem. 1989, 111, b) Chen. M. S.; White, M. C. Science 2007, 318,
18 Curci method s proposed mechanism I II III
19 Curci method 90 min 90 % yield (77) (7) (16) 2 min 97 % yield (58) (42) 80 min 96 % yield 10 % conversion 10 min 95 % yield 14 % conversion
20 White s method Electronic: Me White's catalyst (5 mol %) Ac (50 mol %) 2 2 (1.2 eq) C 3 C, rt, 30 min 48 % Me 17 % Steric: Me White's catalyst (5 mol %) Ac (50 mol %) 2 2 (1.2 eq) C 3 C, rt, 30 min 27 % Me 41 % Directed: White's catalyst (5 mol %) 2 2 (1.2 eq) C 3 C, rt, 30 min 70% not observed Chen. M. S.; White, M. C. Science 2007, 318,
21 Comparison of selectivity of tertiary C- bond activation CF 3 a b c d White catalyst selective for a. Curci non-selective d a b c This work selective for c.
22 Conclusion nly method for conversion of alcohols to 1,3-diols. Practical method using simple reagents. Capable of installing hydroxy functionality in a late stage thereby reducing unproductive chemical manipulations.
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