Synthesis 2021; 53(11): 1931-1942
DOI: 10.1055/a-1348-4242
paper

Synthesis of Polycycles and Oxacycles via Tandem Metathesis of endo-Norbornene Derivatives

Sambasivarao Kotha
,
Sunil Pulletikurti
,
Ambareen Fatma
,
Gopal Dhangar
,
Gonna Somu Naidu
We are thankful to the Department of Science and Technology, Ministry of Science and Technology, India (New Delhi) (EMR/2015/002053), and CSIR (New Delhi) (02(0272)/16/EMR-II) for financial support. S.P. and A.F. thanks University Grants Commission (New Delhi) for financial support and the awarding of a SRF. G.D. and G.S.N. thank Indian Institute of Technology Bombay for the award of post-doctoral fellowship. S.K. thanks the Department of Science and Technology, Ministry of Science and Technology, India (New Delhi) for the awarding of a J. C. Bose fellowship (SR/S2/JCB-33/2010).


Abstract

Here, we have demonstrated that the presence of a carbonyl group at C7 position prevents the olefin metathesis of endo-norbornene derivatives due to complexation of the metal alkylidene. Time-dependent NMR studies showed the presence of new proton signals in the metal alkylidene region, which indicate the formation of metal complex with the carbonyl group of the substrate. These observations were further proved by ESI-MS analysis. Whereas computational studies showed that the catalyst was interacting with the C7 carbonyl group and aligned perpendicular to that of norbornene olefin. These endo-keto norbornene derivatives were reduced to hydroxyl derivatives dia­stereoselectively. Ring-rearrangement metathesis (RRM) of these hydroxyl derivatives, produced the [6/5/6], and [5/6/5] carbo-tricyclic cores of natural products in one step. Whereas the RRM of O-allyl derivatives, delivered the oxa-tricyclic compounds in a single step with excellent yields.

Supporting Information



Publication History

Received: 06 January 2021

Accepted after revision: 08 January 2021

Accepted Manuscript online:
08 January 2021

Article published online:
02 February 2021

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