Reduction of Carbonyl Compounds and Imines Using the CuCl2·2H2O-Li-DTBB (Cat.) Combination

Francisco Alonso; Cristian Vitale; Gabriel Radivoy; Miguel Yus

doi:10.1055/s-2003-37357

PAPER

Reduction of Carbonyl Compounds and Imines Using the CuCl₂·2H₂O-Li-DTBB (Cat.) Combination

Francisco Alonso^a, Cristian Vitale^b, Gabriel Radivoy*^b, Miguel Yus*^a
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Fax: +34(96)5903549; e-Mail: yus@ua.es;
Instituto de Investigaciones en Química Orgánica (INIQO), Departamento de Química, Universidad Nacional del Sur, Avda. Alem 1253, 8000 Bahía Blanca, Argentina
Fax: +54(29)14595187; e-Mail: gradivoy@criba.edu.ar;

Abstract

Alle Artikel dieser Rubrik

Abstract

The reaction of different carbonyl compounds and imines with a mixture of copper(II) chloride dihydrate, an excess of lithium sand, and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 5 mol%) in THF at room temperature, led to the formation of the corresponding alcohols and amines, respectively. The process was also applied to the transformation of α,β-unsaturated carbonyl compounds into the corresponding saturated alcohols. The use of the deuterated copper salt CuCl₂·2D₂O allowed the preparation of the corresponding deuterated products.

Key words

ketones - aldehydes - imines - reductions - copper - alcohols - amines

Volltext

Referenzen

References

<A NAME="RZ14602SS-1A">1a</A> Comprehensive Organic Synthesis Vol. 8: Trost BM. Fleming I. Pergamon Press; Oxford: 1991. Chap. 1.1-1.8.

<A NAME="RZ14602SS-1B">1b</A> Hudlicky M. Reductions in Organic Chemistry 2nd Ed.: American Chemical Society; Washington DC: 1996.

<A NAME="RZ14602SS-2A">2a</A> Alonso F. Yus M. Tetrahedron Lett. 1996, 37: 6925

<A NAME="RZ14602SS-2B">2b</A> Alonso F. Yus M. J. Chem. Educ. 2001, 78: 1517

<A NAME="RZ14602SS-2C">2c</A> Alonso F. Yus M. Tetrahedron Lett. 1997, 38: 149

<A NAME="RZ14602SS-2D">2d</A> Alonso F. Yus M. Tetrahedron 1998, 54: 1921

<A NAME="RZ14602SS-2E">2e</A> Alonso F. Radivoy G. Yus M. Tetrahedron 1999, 55: 4441

<A NAME="RZ14602SS-2F">2f</A> Radivoy G. Alonso F. Yus M. Tetrahedron 1999, 55: 14479

<A NAME="RZ14602SS-2G">2g</A> Alonso F. Radivoy G. Yus M. Tetrahedron 2000, 56: 8673

<A NAME="RZ14602SS-2H">2h</A> Radivoy G. Alonso F. Yus M. Synthesis 2001, 427

<A NAME="RZ14602SS-3">3</A> For the LiAlH₄ conjugate reduction of α,β-unsaturated carbonyl compounds catalysed by CuI, see: Tsuda T. Fujii T. Kawasaki K. Saegusa T. J. Chem. Soc., Chem. Commun. 1980, 1013

For the conjugate reduction of α,β-unsaturated carbonyl compounds mediated by Stryker’s reagent, [(Ph₃P)CuH]₆, see:

<A NAME="RZ14602SS-4A">4a</A> Mahoney WS. Brestensky DM. Stryker JM. J. Am. Chem. Soc. 1988, 110: 291

<A NAME="RZ14602SS-4B">4b</A> Brestensky DM. Stryker JM. Tetrahedron Lett. 1989, 30: 5677

<A NAME="RZ14602SS-4C">4c</A> Mahoney WS. Stryker JM. J. Am. Chem. Soc. 1989, 111: 8818

<A NAME="RZ14602SS-4D">4d</A> Koenig TM. Daeuble JF. Brestensky DM. Stryker JM. Tetrahedron Lett. 1990, 31: 3237

<A NAME="RZ14602SS-4E">4e</A> Lipshutz BH. Keith J. Papa P. Vivian R. Tetrahedron Lett. 1998, 39: 4627

<A NAME="RZ14602SS-4F">4f</A> Lipshutz BH. In Modern Organocopper Chemistry Krause N. Wiley-VCH; Weinheim: 2002.

For the copper(I) salt-mediated conjugate reduction of α,β-unsaturated carbonyl compounds using hydrosilanes, see:

<A NAME="RZ14602SS-5A">5a</A> Ito H. Ishizuka T. Arimoto K. Miura K. Hosomi A. Tetrahedron Lett. 1997, 38: 8887

<A NAME="RZ14602SS-5B">5b</A> Mori A. Fujita A. Nishihara Y. Hiyama T. Chem. Commun. 1997, 2159

<A NAME="RZ14602SS-5C">5c</A> Mori A. Fujita A. Kajiro H. Nishihara Y. Hiyama T. Tetrahedron 1999, 55: 4573

<A NAME="RZ14602SS-5D">5d</A> Appella DH. Moritani Y. Shintani R. Ferreira EM. Buchwald SL. J. Am. Chem. Soc. 1999, 121: 9473

<A NAME="RZ14602SS-5E">5e</A> Moritani Y. Appella DH. Jurkauskas V. Buchwald SL. J. Am. Chem. Soc. 2000, 122: 6797

<A NAME="RZ14602SS-6">6</A> For the conjugate catalytic hydrogenation of α,β-unsaturated carbonyl compounds with Cu/SiO₂, see: Ravasio N. Antenori M. Gargano M. Mastrorilli P. Tetrahedron Lett. 1996, 37: 3529

<A NAME="RZ14602SS-7A">7a</A> Adkins H. Connor R. J. Am. Chem. Soc. 1931, 53: 1091

<A NAME="RZ14602SS-7B">7b</A> Davies RR. Hodgson HH. J. Chem. Soc. 1943, 281

<A NAME="RZ14602SS-7C">7c</A> Montgomery SR. inventors; DE Patent, 2246382. ; Chem. Abstr. 1973, 79, 23974

<A NAME="RZ14602SS-8A">8a</A> Noubi GA. El-Shahed MF. El-Cheikh F. Mansour H. Indian J. Chem., Sect. A 1979, 17: 564

<A NAME="RZ14602SS-8B">8b</A> Mansour H. J. Electrochem. Soc. India 1984, 33: 37

<A NAME="RZ14602SS-8C">8c</A> Raoult E. Sarrazin J. Tallec A. Bull. Soc. Chim. Fr. 1985, 1200

<A NAME="RZ14602SS-8D">8d</A> Bukhtiarov AV. Lebedev AV. Kudryavtsev YuG. Golyshin VN. Zh. Obshch. Khim. 1990, 60: 1325 ; Chem. Abstr. 1990, 113, 220070

<A NAME="RZ14602SS-9">9</A> Fleet GWJ. Harding PJC. Tetrahedron Lett. 1981, 22: 675

<A NAME="RZ14602SS-10">10</A> Sarkar A. Rao BR. Ram B. Synth. Commun. 1993, 23: 291

<A NAME="RZ14602SS-11A">11a</A> Yoon NM. Sim TB. Bull. Korean Chem. Soc. 1993, 14: 749

<A NAME="RZ14602SS-11B">11b</A> Sim TB. Yoon NM. Bull. Chem. Soc. Jpn. 1997, 70: 1101

<A NAME="RZ14602SS-12">12</A> Ito H. Yamanaka H. Ishizuka T. Tateiwa J. Hosomi A. Synlett 2000, 479

<A NAME="RZ14602SS-13A">13a</A> Chen J.-X. Daeuble JF. Brestensky DM. Stryker JM. Tetrahedron 2000, 56: 2153

<A NAME="RZ14602SS-13B">13b</A> Chen J.-X. Daeuble JF. Stryker JM. Tetrahedron 2000, 56: 2789

<A NAME="RZ14602SS-14">14</A> Ravasio N. Psaro R. Zaccheria F. Tetrahedron Lett. 2002, 43: 3943

<A NAME="RZ14602SS-15">15</A> Azzem MA. Mohamed ZF. Fahmy HM. J. Electroanal. Chem. 1995, 399: 121

<A NAME="RZ14602SS-16">16</A> For examples of carbonyl compound reduction with sodium borodeuteride, see for instance: Erb WT. Jones JR. Lu S.-Y. J. Chem. Res., Synop. 1999, 728

<A NAME="RZ14602SS-17">17</A> Perrin DD. Armarego WLF. Purification of Laboratory Chemicals Pergamon Press; Oxford: 1988.

<A NAME="RZ14602SS-18">18</A> Taguchi K. Westheimer FH. J. Org. Chem. 1971, 36: 1570

<A NAME="RZ14602SS-19">19</A> Sandler SR. Karo W. Organic Functional Group Preparations Vol. 12-II: Academic Press; New York: 1971. p.255

<A NAME="RZ14602SS-20">20</A> Layer RW. Chem. Rev. 1963, 63: 489

<A NAME="RZ14602SS-21">21</A> Jacobson SE. Muccigrosso DA. Mares F. J. Org. Chem. 1979, 44: 921

<A NAME="RZ14602SS-22">22</A> Dictionary of Organic Compounds Vol. 1: Chapman and Hall; New York: 1982. p.925

<A NAME="RZ14602SS-23">23</A> Unni MPK. Sreekumar C. Hariharakrishnan VS. Pillai CN. J. Catal. 1978, 53: 168

<A NAME="RZ14602SS-24">24</A> Dictionary of Organic Compounds Vol. 2: Chapman and Hall; New York: 1982. p.2337

<A NAME="RZ14602SS-25">25</A> Puckova LI. Enikeeva NG. Ivanova EV. Kikaeva TG. Golovnya RV. Zhuravleva IL. Izv. Vyssh. Uchebn. Zaved., Pishch. Tekhnol. 1989, 47 ; Chem. Abstr. 1991, 5087

<A NAME="RZ14602SS-26">26</A> Coles N. Harris MCJ. Whitby RJ. Blagg J. Organometallics 1994, 13: 190

<A NAME="RZ14602SS-27">27</A> Sivova LI. Sivov NA. Gracheva RA. Potapov VM. Zh. Org. Khim. 1978. 14: p.791 ; Chem. Abstr. 1978, 42612