Abstract
1,5-C ,C -Cycloalkylation of tert -butyl acetoacetate (1 ) with cis -1,4-dichloro-2-butene (2 ) followed by the haloform reaction of the product in NaOH solution and subsequent
Curtius degradation in tert -butyl alcohol furnished tert -butyl 1-tert -butoxycarbonylaminocyclopent-3-enecarboxylate (5 ) in 32% overall yield.
Key words
alkenes - cyclizations - excitatory amino acids - haloform reaction - Curtius rearrangement
References
<A NAME="RT03404SS-1">1 </A>
Moloney MG.
Nat. Prod. Rep.
2002,
19:
597 ; and references cited therein
<A NAME="RT03404SS-2">2 </A>
Moher ED,
Monn JA, and
Pedregal-Tercero C. inventors; (Eli Lilly and Company); US Pat. WO 2003104217.
; Chem. Abstr . 2004 , 140 , 42463. A financial reward was also offered by InnoCentive for an efficient synthetic
route to this compound (challenge 3100). No solution has ever been accepted; however,
the collected ideas obviously were used in the patent application cited above
<A NAME="RT03404SS-3A">3a </A>
Dias EL.
Nguyen ST.
Grubbs RH.
J. Am. Chem. Soc.
1997,
119:
3887
<A NAME="RT03404SS-3B">3b </A>
Cetinkaya B.
Demir S.
Oezdemir I.
Toupet L.
Semeril D.
Bruneau C.
Dixneuf PH.
Chem.-Eur. J.
2003,
9:
2323
<A NAME="RT03404SS-3C">3c </A>
Wybrow RAJ.
Johnson LA.
Auffray B.
Moran WJ.
Adams H.
Harrity JPA.
Tetrahedron Lett.
2002,
43:
7851
<A NAME="RT03404SS-3D">3d </A>
Connon SJ.
Blechert S.
Bioorg. Med. Chem. Lett.
2002,
12:
1873
<A NAME="RT03404SS-3E">3e </A>
Gibson SE.
Swamy VM.
Adv. Synth. Catal.
2002,
344:
619
<A NAME="RT03404SS-3F">3f </A>
Kotha S.
Sreenivasachary N.
Bioorg. Med. Chem. Lett.
1998,
8:
257
<A NAME="RT03404SS-3G">3g </A>
Kotha S.
Sreenivasachary N.
Mohanraja K.
Durani S.
Bioorg. Med. Chem. Lett.
2001,
11:
1421
<A NAME="RT03404SS-3H">3h </A>
Hammer K.
Undheim K.
Tetrahedron
1997,
53:
2309
<A NAME="RT03404SS-3I">3i </A>
Cockbain J,
Undheim K, and
Hammer K. inventors; Int. Pat. WO 9830535 A1.
; Chem. Abstr . 1998 , 129 , 136491
<A NAME="RT03404SS-4">4 </A>
Depres J.-P.
Greene AE.
J. Org. Chem.
1984,
49:
928
<A NAME="RT03404SS-5A">5a </A>
Park K.-H.
Olmstead MM.
Kurth MJ.
J. Org. Chem.
1998,
63:
6579
<A NAME="RT03404SS-5B">5b </A>
Park K.-H.
Kurth TH.
Olmstead MM.
Kurth MJ.
Tetrahedron Lett.
2001,
42:
991
<A NAME="RT03404SS-6">6 </A> Review:
O’Donnell MJ.
Aldrichimica Acta
2001,
34:
3
<A NAME="RT03404SS-7">7 </A>
tert -Butyl N -(diphenylmethylene)glycinate is commercially available at a price of 46.60 EUR per
1 g (Aldrich).
<A NAME="RT03404SS-8A">8a </A>
Doller D.
Chackalamannil S.
Stamford A.
McKittrick B.
Czarniecki M.
Bioorg. Med. Chem. Lett.
1997,
7:
1381
<A NAME="RT03404SS-8B">8b </A>
Amori L.
Costantino G.
Marinozzi M.
Pellicciari R.
Gasparini F.
Flor PJ.
Kuhn R.
Vranesic I.
Bioorg. Med. Chem. Lett.
2000,
10:
1447
<A NAME="RT03404SS-8C">8c </A>
Hodgson DM.
Thompson AJ.
Wadman S.
Keats CJ.
Tetrahedron
1999,
55:
10815
<A NAME="RT03404SS-8D">8d </A>
Hodgson DM.
Thompson AJ.
Wadman S.
Tetrahedron Lett.
1998,
39:
3357
<A NAME="RT03404SS-9">9 </A>
The price of methyl tert -butyl malonate is 45.00 EUR for 10 mL (Aldrich).
<A NAME="RT03404SS-10">10 </A>
The price of tert -butyl acetoacetate(1 ) is 43.20 EUR for 500 mL (Aldrich).
<A NAME="RT03404SS-11">11 </A>
cis -1,4-Dichloro-2-butene(2 ) is commercially available at a price of 133.00 EUR for 100 g (Aldrich).
<A NAME="RT03404SS-12A">12a </A>
Weinstock J.
J. Org. Chem.
1961,
26:
3511
<A NAME="RT03404SS-12B">12b </A>
Jendralla H.
Chem. Ber.
1980,
113:
3585
<A NAME="RT03404SS-13">13 </A>
Without tin tetrachloride, the yield was only 17%.
<A NAME="RT03404SS-14">14 </A>
Diphenylphosphoryl azide (DPPA) is commercially available at a price of 136.35 EUR
for 100 g (Aldrich) or else can easily be prepared.15
<A NAME="RT03404SS-15">15 </A>
Shioiri T.
Ninomiya K.
Yamada S.-I.
J. Am. Chem. Soc.
1972,
94:
6203