title: Studies on the Himbert intramolecular arene/allene Diels-Alder cycloaddition. Mechanistic studies and expansion of scope to all-carbon tethers.
abstract: The unusual intramolecular arene/allene cycloaddition described 30 years ago by Himbert permits rapid access to strained polycyclic compounds that offer great potential for the synthesis of complex scaffolds. To more fully understand the mechanism of this cycloaddition reaction, and to guide efforts to extend its scope to new substrates, quantum mechanical computational methods were employed in concert with laboratory experiments. These studies indicated that the cycloadditions likely proceed via concerted processes; a stepwise biradical mechanism was shown to be higher in energy in the cases studied. The original Himbert cycloaddition chemistry is also extended from heterocyclic to carbocyclic systems, with computational guidance used to predict thermodynamically favorable cases. Complex polycyclic scaffolds result from the combination of the cycloaddition and subsequent ring-rearrangement metathesis reactions.
authors: 1102 Natural Sciences II, Department of Chemistry, University of California-Irvine, Irvine, California, 92697-2025, USA.
authors: Yvonne
authors: Y
authors: Schmidt
authors: Jonathan K
authors: JK
authors: Lam
authors: Hung V
authors: HV
authors: Pham
authors: K N
authors: KN
authors: Houk
authors: Christopher D
authors: CD
authors: Vanderwal
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D061565:Cycloaddition Reaction; D008958:Models, Molecular; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000466:Alkadienes; D011083:Polycyclic Compounds; C025947:propadiene; D002244:Carbon
references: Org Lett. 2012 Nov 2;14(21):5566-9
references: 23067058
references: Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
references: 9944570
references: J Am Chem Soc. 2006 Jun 14;128(23):7594-607
references: 16756316
references: Proc Natl Acad Sci U S A. 2004 Aug 17;101(33):11943-8
references: 15232003
references: Angew Chem Int Ed Engl. 2008;47(40):7746-9
references: 18752237
references: Annu Rev Phys Chem. 1995;46:701-28
references: 24341393
references: Chem Sci. 2012;2012(3):1650-1655
references: 22611483
references: Angew Chem Int Ed Engl. 2008;47(40):7592-601
references: 18767086
references: Org Lett. 2007 Apr 12;9(8):1589-92
references: 17378575
references: J Org Chem. 2005 Nov 25;70(24):9828-34
references: 16292812
references: J Phys Chem A. 2008 Feb 14;112(6):1095-9
references: 18211046
references: J Phys Chem A. 2005 Oct 27;109(42):9542-53
references: 16866406
references: Org Lett. 2009 Mar 19;11(6):1229-31
references: 19215105
references: J Am Chem Soc. 2011 Mar 23;133(11):3895-905
references: 21351736
references: J Comput Chem. 2003 Apr 30;24(6):669-81
references: 12666158
references: J Org Chem. 2011 Dec 2;76(23):9555-67
references: 21877712