ePrints@IIScePrints@IISc Home | About | Browse | Latest Additions | Advanced Search | Contact | Help

Bromenium-Catalysed Tandem Ring Opening/Cyclisation of Vinylcyclopropanes and Vinylcyclobutanes: A Metal-Free 3+2+1]/4+2+1] Cascade for the Synthesis of Chiral Amidines and Computational Investigation

Ganesh, Venkataraman and Sureshkumar, Devarajulu and Chanda, Debasree and Chandrasekaran, Srinivasan (2012) Bromenium-Catalysed Tandem Ring Opening/Cyclisation of Vinylcyclopropanes and Vinylcyclobutanes: A Metal-Free 3+2+1]/4+2+1] Cascade for the Synthesis of Chiral Amidines and Computational Investigation. In: CHEMISTRY-A EUROPEAN JOURNAL, 18 (39). pp. 12498-12511.

[img] PDF
che_a_eur_jou_18-39_12498_2012.pdf - Published Supplemental Material
Restricted to Registered users only

Download (1288Kb) | Request a copy
[img]
Preview
PDF
chem_201103556_sm_miscellaneous_information.pdf

Download (6Mb) | Preview
Official URL: http://dx.doi.org/10.1002/chem.201103556

Abstract

We present a detailed study of a 3+2+1] cascade cyclisation of vinylcyclopropanes (VCP) catalysed by a bromenium species (Brd+?Xd-) generated in situ, which results in the synthesis of chiral bicyclic amidines in a tandem one-pot operation. The formation of amidines involves the ring-opening of VCPs with Br?X, followed by a Ritter-type reaction with chloramine-T and a tandem cyclisation. The reaction has been further extended to vinylcyclobutane systems and involves a 4+2+1] cascade cyclisation with the same reagents. The versatility of the methodology has been demonstrated by careful choice of VCPs and VCBs to yield bicyclo4.3.0]-, -4.3.1]- and -4.4.0]amidines in enantiomerically pure form. On the basis of the experimental observations and DFT calculations, a reasonable mechanism has been put forth to account for the formation of the products and the observed stereoselectivity. We propose the existence of a p-stabilised homoallylic carbocation at the cyclopropane carbon as the reason for high stereoselectivity. DFT studies at B3LYP/6-311+G** and M06-2X/6-31+G* levels of theory in gas-phase calculations suggest the ring-opening of VCP is initiated at the p-complex stage (between the double bond and Br?X). This can be clearly perceived from the solution-phase (acetonitrile) calculations using the polarisable continuum model (PCM) solvation model, from which the extent of the ring opening of VCP was found to be noticeably high. Studies also show that the formation of zero-bridge bicyclic amidines is favoured over other bridged bicyclic amidines. The energetics of competing reaction pathways is compared to explain the product selectivity.

Item Type: Journal Article
Additional Information: Copyright for this article belongs to WILEY-V C H VERLAG GMBH
Keywords: bromine;chirality;cyclization;vinylcyclobutanes;vinylcyclopropanes
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 12 Nov 2012 09:04
Last Modified: 12 Nov 2012 09:04
URI: http://eprints.iisc.ernet.in/id/eprint/45325

Actions (login required)

View Item View Item