Cobalt(II) Chloride Hexahydrate-Diisopropylamine Catalyzed Mild and Chemoselective Reduction of Carboxylic Esters with Sodium Borohydride

Abstract

The cobalt-catalyzed reduction of unsaturated α-cyano carboxylic esters using sodium borohydride (NaBH₄) leads to the corresponding saturated cyano alcohols in high yields. In particular, the new catalytic system cobalt(II) chloride-diisopropylamine in combination with NaBH₄ showed excellent activity in the chemoselective reduction of a variety of carboxylic esters to their corresponding alcohols in good to excellent yields under mild conditions.

reductions - amines - catalysis - esters - alcohols

References

<A NAME="RT12508SS-1A">1a</A> Brown HC. Hydroboration   W. A. Benjamin, Inc.; New York: 1962. 

<A NAME="RT12508SS-1B">1b</A> Carey FA. Sundberg RJ. Advanced Organic Chemistry   3rd ed., Part A:  Plenum; New York: 1990. 

<A NAME="RT12508SS-2">2</A> For a review, see: Ganem B. Osby JO. Chem. Rev.  1986,  86:  763 

<A NAME="RT12508SS-3A">3a</A> Yang C. Pittman CU. Synth. Commun.  1998,  28:  2027 

<A NAME="RT12508SS-3B">3b</A> Narasimhan S. Balakumar R. Aldrichimica Acta  1998,  31:  19 

<A NAME="RT12508SS-3C">3c</A> Narasimhan S. Madhavan S. Prasad KG. J. Org. Chem.  1995,  60:  5314 

<A NAME="RT12508SS-4">4</A> Qiu Y.-C. Zhang F.-L. Zhang C.-N. Tetrahedron Lett.  2007,  48:  7595 

<A NAME="RT12508SS-5">5</A> Suseela Y. Periasamy M. Tetrahedron  1992,  48:  371 

<A NAME="RT12508SS-6">6</A> Abiko A. Masamune S. Tetrahedron Lett.  1992,  33:  5517 

<A NAME="RT12508SS-7">7</A> Kanth JVB. Periasamy M. J. Org. Chem.  1991,  56:  5964 

<A NAME="RT12508SS-8">8</A> Lane CF. Myatt HL. Daniels J. Hopps HB. J. Org. Chem.  1974,  39:  3052 

<A NAME="RT12508SS-9">9</A> For a review, see: Periasamy M. Thirumalaikumar M. J. Organomet. Chem.  2000,  609:  137 

<A NAME="RT12508SS-10A">10a</A> da Costa JCS. Pais KC. Fernandes EL. de Oliveira PSM. Mendonça JS. de Souza MVN. Peralta MA. Vasconcelos TRA. ARKIVOC  2006,  (i):  128 

<A NAME="RT12508SS-10B">10b</A> Boechat N. da Costa JCS. Mendonça JS. de Oliveira PSM. de Souza MVN. Tetrahedron Lett.  2004,  45:  6021 

<A NAME="RT12508SS-10C">10c</A> Zhu HJ. Pittman CU. Synth. Commun.  2003,  33:  1733 

<A NAME="RT12508SS-10D">10d</A> Santaniello E. Ferraboschi P. Sozzani P. J. Org. Chem.  1981,  46:  4584 

<A NAME="RT12508SS-10E">10e</A>

See also ref. 3a.

<A NAME="RT12508SS-10F">10f</A> Guida WC. Entreken EE. Guida AR. J. Org. Chem.  1984,  49:  3024 

<A NAME="RT12508SS-11A">11a</A> Das D. Roy S. Das PK. Org. Lett.  2004,  6:  4133 

<A NAME="RT12508SS-11B">11b</A> Kokotos G. Noula C. J. Org. Chem.  1996,  61:  6994 

<A NAME="RT12508SS-11C">11c</A> Meschino JA. Bond CH. J. Org. Chem.  1963,  28:  3129 

<A NAME="RT12508SS-11D">11d</A> Poos GI. Carson JR. Rosenau JD. Roszkowski AP. Kelley NM. McGowin J. J. Med. Chem.  1963,  6:  266 

<A NAME="RT12508SS-11E">11e</A> Fodor G. Koczka K. J. Chem. Soc.  1952,  850 

<A NAME="RT12508SS-12A">12a</A> Li L.-C. Jiang J.-X. Ren J. Ren Yi. Pittman CU. Zhu H.-J. Eur. J. Org. Chem.  2006,  1981 

<A NAME="RT12508SS-12B">12b</A> Patra A. Batra S. Bhaduri AP. Synlett  2003,  1611 

<A NAME="RT12508SS-12C">12c</A> Corrêa IR. Moran JS. Tetrahedron  1999,  55:  14221 

<A NAME="RT12508SS-12D">12d</A> Dalla V. Catteaua JP. Pale P. Tetrahedron Lett.  1999,  40:  5193 

<A NAME="RT12508SS-12E">12e</A> Lanier M. Pastor R. Tetrahedron Lett.  1995,  36:  2491 

<A NAME="RT12508SS-13A">13a</A> Jagdale AR. Sudalai A. Tetrahedron Lett.  2008,  49:  3790 

<A NAME="RT12508SS-13B">13b</A> Paraskar AS. Sudalai A. Tetrahedron  2006,  62:  4907 

<A NAME="RT12508SS-13C">13c</A> Geiger C. Kreitmeier P. Reiser O. Adv. Synth. Catal.  2005,  347:  249 

<A NAME="RT12508SS-13D">13d</A> Ranu BC. Samanta S. Tetrahedron  2003,  59:  7901 

<A NAME="RT12508SS-13E">13e</A> Ranu BC. Samanta S. J. Org. Chem.  2003,  68:  7130 

<A NAME="RT12508SS-13F">13f</A> Matt PV. Pfaltz A. Tetrahedron: Asymmetry  1991,  2:  691 

<A NAME="RT12508SS-13G">13g</A> Leutenegger U. Madin A. Pfaltz A. Angew. Chem., Int. Ed. Engl.  1989,  28:  60 

<A NAME="RT12508SS-13H">13h</A> Misun M. Pfaltz A. Helv. Chim. Acta  1996,  79:  961 

<A NAME="RT12508SS-13I">13i</A> Brown MS. Rapoport H. J. Org. Chem.  1963,  28:  3261 

<A NAME="RT12508SS-14">14</A> Kadin SB. J. Org. Chem.  1966,  31:  620 

<A NAME="RT12508SS-15A">15a</A> Yamakawa T. Masaki M. Nohira H. Bull. Chem. Soc. Jpn.  1991,  64:  2730 

<A NAME="RT12508SS-15B">15b</A> Lane CF. Aldrichimica Acta  1973,  6:  51