Carbonylation of Doubly Lithiated N′-Aryl-N,N-Dimethylureas: A Novel Approach to Isatins via Intramolecular Trapping of Acyllithiums

Keith Smith; Gamal A. El-Hiti; Anthony C. Hawes

doi:10.1055/s-2003-41019

PAPER

Carbonylation of Doubly Lithiated N′-Aryl-N,N-Dimethylureas: A Novel Approach to Isatins via Intramolecular Trapping of Acyllithiums

Keith Smith*, Gamal A. El-Hiti, Anthony C. Hawes
Centre for Clean Chemistry, Department of Chemistry, University of Wales Swansea, Singleton Park, Swansea, SA2 8PP, UK
Fax: +44(1792)295261; e-Mail: k.smith@swansea.ac.uk;

Abstract

All articles of this category

Abstract

Lithiation of N′-(2-bromoaryl)-N,N-dimethylureas with methyllithium and tert-butyllithium under nitrogen in anhydrous THF at 0 °C gave doubly lithiated arylurea derivatives, which react with carbon monoxide at 0 °C to give isatins in good yields. The scope of the reaction has been demonstrated by application to the synthesis of isatin itself and four substituted isatins bearing alkyl, chloro or fluoro groups.

Key words

carbonylation - N,N-dimethylureas - isatins - intramolecular trapping - positron emission tomography

Full Text

References

Permanent address: G. A. El-Hiti, Department of Chemistry, Faculty of Science, Tanta University, Tanta 31527, Egypt.

<A NAME="RZ07103SS-2A">2a</A> Trzupek LS. Newirth TL. Kelly EG. Sbarbati NE. Whitesides GM. J. Am. Chem. Soc. 1973, 95: 8118

<A NAME="RZ07103SS-2B">2b</A> Narayama C. Periasamy M. Synthesis 1985, 253

<A NAME="RZ07103SS-3A">3a</A> Seebach D. Angew. Chem., Int. Ed. Engl. 1969, 8: 639 ; Angew. Chem. 1969, 81, 690

<A NAME="RZ07103SS-3B">3b</A> Beak P. Reitz DR. Chem. Rev. 1978, 78: 275

<A NAME="RZ07103SS-3C">3c</A> Martin SF. Synthesis 1979, 633

<A NAME="RZ07103SS-3D">3d</A> Albright JD. Tetrahedron 1983, 39: 3207

<A NAME="RZ07103SS-3E">3e</A> Snieckus V. Chem. Rev. 1990, 90: 879

<A NAME="RZ07103SS-3F">3f</A> Anctil EJ.-G. Snieckus V. J. Organomet. Chem. 2002, 653: 150

<A NAME="RZ07103SS-4A">4a</A> Seyferth D. Weinstein DR. J. Am. Chem. Soc. 1982, 104: 5534

<A NAME="RZ07103SS-4B">4b</A> Seyferth D. Weinstein RM. Wang W.-L. J. Org. Chem. 1983, 48: 1144

<A NAME="RZ07103SS-4C">4c</A> Weinstein RM. Wang W.-L. J. Org. Chem. 1983, 48: 3367

<A NAME="RZ07103SS-4D">4d</A> Seyferth D. Weinstein RM. Wang W.-L. Hui RC. Tetrahedron Lett. 1983, 24: 4907

<A NAME="RZ07103SS-4E">4e</A> Seyferth D. Hui RC. Organometallics 1984, 3: 327

<A NAME="RZ07103SS-4F">4f</A> Seyferth D. Hui RC. Tetrahedron Lett. 1984, 25: 5251

<A NAME="RZ07103SS-4G">4g</A> Seyferth D. Weinstein RM. Hui RC. Wang W.-L. Archer CM. J. Org. Chem. 1991, 56: 5768

<A NAME="RZ07103SS-4H">4h</A> Seyferth D. Weinstein RM. Hui RC. Wang W.-L. Archer CM. J. Org. Chem. 1992, 57: 5620

<A NAME="RZ07103SS-5A">5a</A> Nudelman NS. Vitale AA. J. Org. Chem. 1981, 46: 4625

<A NAME="RZ07103SS-5B">5b</A> Seyferth D. Hui RC. Wang W.-L. J. Org. Chem. 1993, 58: 5843

See for example:

<A NAME="RZ07103SS-6A">6a</A> Orita A. Fukudome M. Ohe K. Murai S. J. Org. Chem. 1994, 59: 477

<A NAME="RZ07103SS-6B">6b</A> Orita A. Ohe K. Murai S. Organometallics 1994, 13: 1533

<A NAME="RZ07103SS-6C">6c</A> Kai H. Iwamoto K. Chatani N. Murai S. J. Am. Chem. Soc. 1996, 118: 7634

<A NAME="RZ07103SS-6D">6d</A> Ryu I. Yamamoto H. Sonoda N. Murai S. Organometallics 1996, 15: 5459

<A NAME="RZ07103SS-6E">6e</A> Kai H. Yamauchi M. Murai S. Tetrahedron Lett. 1997, 38: 9027

<A NAME="RZ07103SS-6F">6f</A> Fukuyama T. Chatani N. Kakiuchi F. Murai S. J. Org. Chem. 1997, 62: 5647

<A NAME="RZ07103SS-6G">6g</A> Ryu I. Matsu K. Minakata S. Komatsu M. J. Am. Chem. Soc. 1998, 120: 5838

<A NAME="RZ07103SS-6H">6h</A> Ryu I. Chem. Soc. Rev. 2001, 30: 16

See for example:

<A NAME="RZ07103SS-7A">7a</A> Smith K. El-Hiti GA. Abdo MA. Abdel-Megeed MF. J. Chem. Soc., Perkin Trans. 1 1995, 1029

<A NAME="RZ07103SS-7B">7b</A> Smith K. El-Hiti GA. Abdel-Megeed MF. Abdo MA. J. Org. Chem. 1996, 61: 647

<A NAME="RZ07103SS-7C">7c</A> Smith K. El-Hiti GA. Abdel-Megeed MF. Abdo MA. J. Org. Chem. 1996, 61: 656

<A NAME="RZ07103SS-7D">7d</A> Smith K. El-Hiti GA. Hamilton A. J. Chem. Soc., Perkin Trans. 1 1998, 4041

<A NAME="RZ07103SS-7E">7e</A> Smith K. El-Hiti GA. Abdel-Megeed MF. Abdo MA. Collect. Czech. Chem. Commun. 1999, 64: 515

<A NAME="RZ07103SS-8A">8a</A> Smith K. Pritchard GJ. Angew. Chem., Int. Ed. Engl. 1990, 29: 282 ; Angew. Chem. 1990, 102, 298

<A NAME="RZ07103SS-8B">8b</A> Smith K. El-Hiti GA. Pritchard GJ. Hamilton A. J. Chem. Soc., Perkin Trans. 1 1999, 2299

Smith, K.; El-Hiti, G. A.; Abdel-Megeed, M. F. Russ. J. Org. Chem. 2003, accepted for publication.

<A NAME="RZ07103SS-10">10</A> Smith K. Shukla AP. Matthews I. Sulfur Lett. 1996, 20: 121

<A NAME="RZ07103SS-11">11</A> Smith K. El-Hiti GA. Shukla AP. J. Chem. Soc., Perkin Trans. 1 1999, 2305

<A NAME="RZ07103SS-12">12</A> Smith K. El-Hiti GA. Hawes AC. Synlett 1999, 945

<A NAME="RZ07103SS-13">13</A> Eckert H. Forster B. Angew. Chem., Int. Ed. Engl. 1987, 26: 894

<A NAME="RZ07103SS-14">14</A> Schmitz E. J. Prakt. Chem. 1974, 316: 569

<A NAME="RZ07103SS-15A">15a</A> Bettembourg M.-C. David S. Bull. Soc. Chim. Fr. 1962, 772

<A NAME="RZ07103SS-15B">15b</A> David S. Dauct M.-C. Bull. Soc. Chim. Fr. 1967, 2152

<A NAME="RZ07103SS-15C">15c</A> Franklin CS. White AC. J. Chem. Soc. 1963, 1335

<A NAME="RZ07103SS-15D">15d</A> Bergman J. Tetrahedron 1971, 27: 1167

<A NAME="RZ07103SS-16">16</A> Gassman PG. Cue BW. Luh T.-Y. J. Org. Chem. 1977, 42: 1344

<A NAME="RZ07103SS-17">17</A> O’Sullivan DG. Sadler PW. J. Chem. Soc. 1956, 2202

<A NAME="RZ07103SS-18">18</A> Agdepy ED. Kepe V. Petri A. Satyamurthy N. Liu J. Huang S.-C. Small GW. Cole GM. Barrio JR. Neuroscience 2003, 117: 723

<A NAME="RZ07103SS-19">19</A> Watson SC. Eastham JF. J. Organomet. Chem. 1967, 9: 165

<A NAME="RZ07103SS-20">20</A> Vogel’s Textbook of Practical Organic Chemistry 5th ed.: Longman; Harlow: 1989.

<A NAME="RZ07103SS-21">21</A> Perrin DD. Armarego WLF. Perrin DR. Purification of Laboratory Chemicals 3rd ed.: Pergamon, Butterworth Heinemann; Oxford: 1988.