Abstract
A highly convenient way to perform the synthesis of alkynes from aldehydes is reported.
The procedure utilizes a new in situ preparation of dimethyldiazomethylphosphonate.
As a consequence a commercially available reagent can now be used, circumventing a
disadvantage of earlier protocols. The easy one-pot procedure avoids the use of strong
bases, low temperatures and inert gas techniques.
Key words
alkynes - phosphonates - rearrangements
References <A NAME="RZ12003SS-1">1 </A>
New address: Boehringer Ingelheim Pharma GmbH & Co. KG, Chemical Research, Birkendorfer
Str. 65, 88397 Biberach/Riss, Germany.
<A NAME="RZ12003SS-2">2 </A>
New address: Abbott GmbH & Co. KG, Knollstr., 67061 Ludwigshafen, Germany.
3a </A>
Seyferth D.
Marmor RS.
Hilbert P.
J. Org. Chem.
1971,
36:
1379
3b </A>
Lewis RT.
Motherwell BT.
Tetrahedron
1992,
48:
1465
3c </A>
Brown DG.
Velthuisen EJ.
Commerford JR.
Brisbois RG.
Hoye TR.
J. Org. Chem.
1996,
61:
2540
4a </A>
Gilbert JC.
Weerasoriya U.
J. Org. Chem.
1979,
44:
4997
4b </A>
Gilbert JC.
Weerasoriya U.
J. Org. Chem.
1982,
47:
1837
<A NAME="RZ12003SS-5">5 </A>
Corey EJ.
Fuchs PL.
Tetrahedron Lett.
1972,
3769
6a </A>
Köbrich G.
Trapp H.
Flory K.
Drischel W.
Chem. Ber.
1966,
99:
689
6b </A>
Bestmann HJ.
Frey H.
Liebigs Ann. Chem.
1980,
2061
6c </A>
Corey EJ.
Achiwa K.
Katzenellenbogen JA.
J. Am. Chem. Soc.
1969,
91:
4318
6d </A>
Matsumoto M.
Kuroda K.
Tetrahedron Lett.
1980,
21:
4021
6e </A>
Bestmann HJ.
Rippel H.
Dostalek R.
Tetrahedron Lett.
1989,
30:
5261
<A NAME="RZ12003SS-7">7 </A> For the use of trimethylsilyldiazomethane as reagent, see:
Ohira S.
Okai K.
Moritani T.
J. Chem. Soc., Chem. Commun.
1992,
721 ; and ref. cited therein
8a </A>
Regitz M.
Anschütz W.
Liebigs Ann. Chem.
1969,
730:
194
8b </A>
Regitz M.
Liedhegener A.
Eckstein U.
Martin M.
Anschütz W.
Liebigs Ann. Chem.
1971,
748:
207
<A NAME="RZ12003SS-9">9 </A>
Colvin EW.
Hamill BJ.
J. Chem. Soc., Perkin Trans. 1
1977,
869
<A NAME="RZ12003SS-10">10 </A>
Müller S.
Liepold B.
Roth GJ.
Bestmann HJ.
Synlett
1996,
521
<A NAME="RZ12003SS-11">11 </A>
Ohira S.
Synth. Commun.
1989,
19:
561
<A NAME="RZ12003SS-12">12 </A>
Callant P.
D’Haenens L.
Vandewalle M.
Synth.Commun.
1984,
14:
155
<A NAME="RZ12003SS-13">13 </A> This protocol has been used for the diazotation of β-ketoesters:
Koskinen AMP.
Muñoz L.
J. Chem. Soc., Chem. Commun.
1990,
652
<A NAME="RZ12003SS-14">14 </A>
Brands KMJ. inventors; UK Pat. Appl., GB 2355988A. Researchers from Merck reported the
successful use of azidotris(diethylamino)phosphonium bromide for this purpose:
; Chem. Abstr. 2001 , 135 , 152576
<A NAME="RZ12003SS-15">15 </A>
Fett D.
PhD Thesis
Universität Erlangen-Nürnberg;
Germany:
1995.
<A NAME="RZ12003SS-16">16 </A>
Müller S.
PhD Thesis
Universität Erlangen-Nürnberg;
Germany:
1996.
<A NAME="RZ12003SS-17">17 </A> Compound 5e has been prepared before utilizing the conditions of the old Method B:
Böhmer J.
Hampel F.
Schobert R.
Synthesis
1997,
661
<A NAME="RZ12003SS-18">18 </A>
Hafner K.
Bernhard C.
Liebigs Ann. Chem.
1959,
625:
108
<A NAME="RZ12003SS-19">19 </A>
Krämer CS.
Zeitler K.
Müller TJJ.
Org. Lett.
2000,
2:
3723
<A NAME="RZ12003SS-20">20 </A>
Regitz M.
Hocker J.
Liedhegener A.
Org. Synth., Coll. Vol. V
Wiley;
New York:
1973.
p.179
<A NAME="RZ12003SS-21">21 </A>
Sugiyama S.
Honda M.
Komori T.
Liebigs Ann. Chem.
1990,
1069
<A NAME="RZ12003SS-22">22 </A>
Brown RFC.
Eastwood FW.
Harrington KJ.
McMullen GL.
Aust. J. Chem.
1974,
27:
2393
<A NAME="RZ12003SS-23">23 </A>
Snider BB.
Killinger TA.
J. Org. Chem.
1978,
43:
2161
<A NAME="RZ12003SS-24">24 </A>
Purification by column chromatography.
