Diastereoselective Synthesis of Three-, Five-, Six-, and Seven-Membered Rings from Fischer Carbene Complexes and 4-Unsubstituted 1-Amino-1,3-Dienes

✍ Scribed by Fernando Aznar; Martín Fañanás-Mastral; Jorge Alonso; Francisco J. Fañanás

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 316 KB
• Volume: 14
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200701109

✦ Synopsis

Abstract

Fischer carbene complexes react with 4‐unsubstituted 1‐amino‐1,3‐dienes to give different carbocyclization products depending on the nature of the carbene complex and on the substitution pattern of the aminodiene. Thus, the reaction of arylcarbene chromium complexes and 1‐aminodienes diastereoselectively affords cyclopropane derivatives by means of a formal [2+1] carbocyclization reaction. In particular, pentacarbonyl[(2‐furyl)(methoxy)methylene]chromium complex furnishes formal [4+1] carbocyclization products. Starting from β‐substituted alkenylcarbene complexes, formal [4+1] reactions occur and cyclopentenamine derivatives are diastereoselectively formed. However, when the α,β‐disubstituted alkenylcarbene complex pentacarbonyl[(5,6‐dihydro‐2__H__‐pyran‐2‐yl)(methoxy)methylene]tungsten is used, the outcome of the reaction depends on the substitution on the carbon atom at the 3‐position of the aminodiene, generating the [3+2] or [4+3]‐cyclization products if the substituent is or is not a hydrogen atom, respectively. Finally, when the reaction is performed with alkynylcarbene complexes, benzaldehyde derivatives are obtained if the triple‐bond substituent is a phenyl group or indene derivatives if the group is an alkenyl moiety.