Facile and Chemo-selective Cleavages of Allyl Ethers Utilizing Tetrabutylammonium Sulfate Radical Species

Abstract

Allyl ethers containing various functional groups reacted with tetrabutylammonium peroxydisulfate in acetonitrile under mild conditions to afford the corresponding cleaved alcohols in excellent yields.

cleavage of allyl ethers - tetrabutylammonium peroxydisulfate - chemo-selectivity - deprotection

References

<A NAME="RY22901ST-1">1</A> Cunninghan J. Gigg R. Warren CD. Tetrahedron Lett.  1964,  1191 

<A NAME="RY22901ST-2">2</A> Guibe F. Tetrahedron  1997,  53:  13509 

For pertinent monographs, see:

<A NAME="RY22901ST-3A">3a</A> Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   2nd ed.:  Wiley; New York: 1991. 

<A NAME="RY22901ST-3B">3b</A> Kocienski PJ. Protecting Groups   Thieme; Stuttgart: 1994. 

<A NAME="RY22901ST-4A">4a</A> Gent PA. Grigg R. J. Chem. Soc., Chem. Commun.  1974,  277 

<A NAME="RY22901ST-4B">4b</A> Grigg R. J. Chem. Soc., Perkin Trans. 1  1980,  738 

<A NAME="RY22901ST-5">5</A> Grigg J. Grigg R. J. Chem. Soc., Chem. Commun.  1966,  82 

<A NAME="RY22901ST-6A">6a</A> Espanet B. Bunach E. Perichon Y. Tetrahedron Lett.  1992,  33:  2485 

<A NAME="RY22901ST-6B">6b</A> Kadam SM. Nayak SK. Banerji A. Tetrahedron Lett.  1992,  33:  5129 

<A NAME="RY22901ST-6C">6c</A> Mereyala HB. Guntha S. Tetrahedron Lett.  1993,  34:  6929 

<A NAME="RY22901ST-6D">6d</A> Ito H. Taguchi T. Hazawa Y. J. Org. Chem.  1993,  58:  774 

<A NAME="RY22901ST-6E">6e</A> Diaz RR. Melagatejo CR. Lopez-Espinosa MTP. Cubero II. J. Org. Chem.  1994,  59:  7928 

<A NAME="RY22901ST-6F">6f</A> Lee J. Cha JK. Tetrahedron Lett.  1996,  37:  3663 

<A NAME="RY22901ST-6G">6g</A> Honda M. Morita H. Nagaku I. J. Org. Chem.  1997,  62:  8932 

<A NAME="RY22901ST-6H">6h</A> Yu B. Li B. Zhang J. Hui Y. Tetrahedron Lett.  1998,  39:  4871 

<A NAME="RY22901ST-7">7</A> Taniguchi T. Ogasawara K. Angew. Chem. Int. Ed.  1998,  37:  1136 

<A NAME="RY22901ST-8">8</A>

The allyl ether containing aldehyde moiety 2m reacted with DIBAL-H (1 equiv) in the presence of NiCl₂[dppp] in the short reaction time (30 min) resulted in the corresponding alcohols as shown below (Equation 5).

Equation 5

<A NAME="RY22901ST-9">9</A> Yadav JS. Chardrasekhar S. Sumitra G. Kacke R. Tetrahedron Lett.  1996,  37:  6603 

<A NAME="RY22901ST-10A">10a</A> Jung JC. Choi HC. Kim YH. Tetrahedron Lett.  1993,  34:  3581 

<A NAME="RY22901ST-10B">10b</A> Choi HC. Kim YH. Synth. Commun.  1994,  24:  2307 

<A NAME="RY22901ST-10C">10c</A> Choi HC. Cho KI. Kim YH. Synlett  1995,  207 

<A NAME="RY22901ST-10D">10d</A> Yang SG. Lee DH. Kim YH. Heteroat. Chem.  1997,  8:  435 

<A NAME="RY22901ST-10E">10e</A> Hwang JP. Yang SG. Kim YH. Chem. Commun.  1997,  1355 

<A NAME="RY22901ST-10F">10f</A> Kim YH. Hwang JP. Yang SG. Tetrahedron Lett.  1997,  38:  3009 

<A NAME="RY22901ST-11">11</A>

The aldehyde 4 was isolated (80%) and confirmed through GC analysis by comparison with the authentic sample of acrolein.