Our Research Contributions in Brief
Towards development of the Baylis-Hillman reaction as a powerful synthetic tool in organic chemistry
I joined the School of Chemistry, University of Hyderabad in June 1984. Since then we have focused our research work on Baylis-Hillman (BH) patent and undertaken a long term research program with an objective of developing this reaction (Fig. 1.) from unknown patent level (buried in the literature) to the level of high popularity and utility. We have thus been working in this direction for the past 33 + years and made original and fundamental contributions that brought this reaction to the fore-front of synthetic chemistry- for more information see Chimia 2013, 67, 8-16.
Fundamental contributions toward development of Baylis-Hillman reaction
Our research group has made pioneering contributions for the growth of the Baylis-Hillman reaction in all the directions: i) In expanding the scope of all the three essential components, ii) asymmetric version, iii) two component Baylis-Hillman reaction and iv) intramolecular BH reaction [see selected publications: (1) Tetrahedron Lett. 1986, 27, 2031-2032; (2) Tetrahedron Lett. 1987, 28, 4351-4352; (3) Tetrahedron Lett. 1987, 28, 4591-4592; (4) Synth. Commun. 1987, 17, 587-591; (5) Synth. Commun. 1987, 17, 1893-1896; (6) Tetrahedron Lett. 1990, 31, 1621-1624; (7) Tetrahedron Lett. 2001, 42, 85-87; (8) Synth. Commun. 2001, 31, 2987-2995. (9) Chem. Commun. 2003, 604-605; (10) J. Org. Chem. 2003, 68, 5983-5991; (11) Tetrahedron, 2010, 66, 5612-5622; (12) Eur. J. Org. Chem. 2014, 1157-1162; (13) Tetrahedron, 2014, 70, 7991-7995; (14) Org. Biomol. Chem. 2014,12,1551-1555; (15) Tetrahedron, 2017, 73, 859-867; (16) Eur. J. Org. Chem. 2017, 5135-5140.].
The Baylis-Hillman reaction is now a well known name reaction. It is a three component, atom-economy carbon-carbon bond forming reaction involving the coupling of α-position of an activated alkene with an electrophile under the influence of a catalyst or catalytic system producing densely functionalized molecules (Fig. 2). BH reaction is one of the best examples for organo-catalytic C-H functionalization processes
Baylis-Hillman adducts: Novel source for discovering new transformations and concepts
The Baylis-Hillman adducts can be envisaged in different ways (six possible ways of viewing these adducts are presented in Fig. 3). Also the BH adducts can be envisioned as a source of various reactive species (Fig. 4). Having visualized the BH adducts as shown in Figs. 3 and 4 we focused our work in these directions. We have shown the potential of BH adducts and also demonstrated the power of proximity of three functional groups that are present in BH adducts [See selected publications: (1) J. Chem. Soc., Chem. Commun. 1992, 955-957; (2) Tetrahedron Lett. 1995, 36, 757-758; (3) Synlett 1996, 393-395; (4) Synlett 1996, 747-748; (5) Tetrahedron Lett. 1997, 38, 2141-2144; (6) Tetrahedron 1998, 54, 4943-4948; (7) Chem. Commun. 1998, 1639-1640; (8) J. Org. Chem. 1999, 64, 1197-1200; (9) Tetrahedron Lett. 2001, 42, 477-479; (10) Tetrahedron Lett. 2001, 42, 3025-3027; (11) Org. Lett. 2001, 3, 3619-3622; (12) Chem. Commun. 2004, 32-33; (13) Tetrahedron Lett. 2004, 45, 1621-1625; (14) J. Org. Chem. 2004, 69, 7379-7382; (15) Org. Lett. 2007, 9, 2453-2456; (16) Org. Biomol. Chem. 2008, 6, 1034-1039; (17) Org. Lett. 2008, 10, 1819-1822; (18) Synlett, 2009, 411-416; (19) Chem. Eur. J. 2010, 16, 2031-2035; (20) Org. Biomol. Chem. 2012, 10, 8774-8777; (21) Chem. Eur. J. 2013, 19, 2961-2965 (22) Eur. J. Org. Chem. 2016, 2398-2403].
We have written three major reviews [(1) Tetrahedron 1996, 52, 8001-8062; (2) Chem. Rev. 2003, 103, 811-891; (3) Chem. Rev. 2010, 110, 5447-5674] and four mini reviews [(1) Chem. Soc. Rev. 2007, 36, 1581-1588; (2) Chem. Soc. Rev. 2012, 41, 68-78; (3) Chimia 2013, 67, 8-16; (4) ARKIVOC 2016, 172-205] highlighting the salient feature of development of BH reaction and future projections on this fascinating reaction. Our mini review in Chimia (Chimia 2013, 67, 8-16) describes accounts of our own work on the Baylis–Hillman reaction. Our research is now focused towards development of single component and multi-BH reactions.
Other Research Areas:
Although the major foucs of our research is the Baylis-Hillman reaction, we have also made significant contributions in the area of biotransformations and chiral catalysis (for asymmetric reductions) see the list of publications
RESEARCH CONTRIBUTIONS IN DETAIL