Author Topic: Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates  (Read 121 times)

mildronate

  • Larvae
  • *
  • Posts: 28
Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates
« on: October 22, 2011, 03:27:41 PM »
Very interesting article, to my mind its future:

Tungsten.

  • Larvae
  • *
  • Posts: 44
Re: Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates
« Reply #1 on: October 22, 2011, 04:00:19 PM »
It seems like it would be far easier to just make the acetone halide and run a Friedel-Crafts which requires AlCl3 instead of palladium. Interesting paper though. It might even be easier to get palladium under certain circumstances.
-W

mildronate

  • Larvae
  • *
  • Posts: 28
Re: Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates
« Reply #2 on: October 22, 2011, 09:27:23 PM »
Fridel is a shit (low yield and need many AlCl3). I found this synth with scifinder.

letters

  • Subordinate Wasp
  • ***
  • Posts: 138
Re: Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates
« Reply #3 on: October 23, 2011, 08:12:33 PM »
friedel crafts is not "shit". not by any reasonable standard, especially if you consider the newer publications. but it does have its drawbacks. the Pd route is very promising since it is far more tolerable to aromatic substituents then friedel crafts (AlCl3 will dealkylate aromatic ethers, even though with proper conditions it is avoided), and it is catalytic. it is obvious, due to the high loadings of the ligand and catalyst (4 and 1%, respectively) that this combination is not ideal. it works well, but when you find the ideal catalyst, the loadings can be 0.1-0.01% Pd. look at the newer generation Buchwald-Hartwig aminations and the "Homeopathic, Ligandless" Heck reactions.

if you can afford the ligand (or make it, but youd probably a positive nitrogen pressure box to work under inert and dry atmosphere) and the catalyst and still stay economical this route is golden!

akcom

  • Dominant Queen
  • ****
  • Posts: 430
alpha aryl ketones from acetone and aryl tosylates
« Reply #4 on: October 28, 2011, 05:30:51 AM »
Palladium-Catalyzed Mono-alpha-arylation of Acetone with Aryl Halidesand Tosylates
Kevin D. Hesp, Rylan J. Lundgren, and Mark Stradiotto
JACS 2011, 133, pg 5194-5197

If you're already buying palladium...

akcom

  • Dominant Queen
  • ****
  • Posts: 430
Re: alpha aryl ketones from acetone and aryl tosylates
« Reply #5 on: October 28, 2011, 05:44:52 AM »
preparation of cinnamyl chloride:
Quote

1-Chloro-3-phenylprop-2-ene.5s Concentrated aqueous HCI (50 mL)
was added over 1 min to a stirred solution of  cinnamyl alcohol (21 g) in
T H F  (50  mL), whereafter  the  solution  became  heterogeneous.  The
mixture was vigorously stirred for  15 min and was then poured into water
and was extracted with CH2CI,.  The CH2CI2 was washed twice with
water, once with aqueous NaHCO,,  with water again, and dried (MgS-
04). On removal of the solvent, a yellow oil remained which was distilled
a t  45 mm  (bp 105 "C) through a  15-cm vacuum-jacketed  Vigreux col-
umn to give 20.4  g of  pure cinnamyl  chlorid

preparation of Pd[(pi-cinnamyl)Cl]2:
Quote
Hz, 1 H) ,  1.38 (s, 3 H ) ,  1.32 (d, J  = 7 Hz, 3 H) ,  1.20 (s, 3 H) . 
Palladium  chloride  (1.77 g) and lithium
chloride (1.77 g) were dissolved in hot water (2.5 mL) and then cinnamyl
chloride (6.2 g) in ethanol (20 mL)  was added. Carbon monoxide was
bubbled through the solution a t  25 OC  and after 15 min orange crystals
began to form and after a total of  3 h, the carbon monoxide flow was
discontinued and the mixture was stirred under carbon monoxide for 20
h a t  25 OC  and for a further 24 h a t  0 OC.  The product was then filtered
and was washed  with methanol followed by ether.  The orange powder
was  recrystallized  from chloroform  by the addition ether  (2.3 g, 90%).

ref:
Asymmetric Synthesis, Asymmetric Catalytic Allylation Using Palladium  Chiral Phosphine Complexes
Pamela R. Auburn, Peter B. Mackenzie, and B. Bosnich
JACS 1985, 107, pg 2033-2046
« Last Edit: October 28, 2011, 05:53:36 AM by akcom »

java

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 783
Re: Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates
« Reply #6 on: October 28, 2011, 03:43:47 PM »
Reference Information


Asymmetric synthesis. Asymmetric catalytic allylation using palladium chiral phosphine complexes
Pamela R. Auburn, Peter B. Mackenzie, B. Bosnich
J. Am. Chem. Soc.,
1985, 107 (7), pp 2033–2046
DOI: 10.1021/ja00293a038
¡Prefiero morir de pie que vivir siempre arrodillado!.Emiliano ZapataIt is better to die on your feet than to live on your knees!.......