Domino Reaction of 2,4-Diyn-1-ols with 1,3-Dicarbonyl Compounds: Direct Access to Aryl/Heteroaryl-Fused Benzofurans and Indoles.

A domino propargylation/furanylation (intramolecular exo-dig-cyclization)/benzannulation reaction of 2,4-diyn-1-ols with 1,3-dicarbonyl compounds has been developed for the first time. This provides a novel and effective method for the preparation of aryl/heteroaryl-fused benzofurans from easily accessible starting materials in a single step. The methodology was extended to pyrrolyl-benzannulation to obtain aryl/heteroaryl-fused indoles. Further, application of this approach in the synthesis of eustifoline D and dictyodendrin structural frameworks has been demonstrated.

Facile access to [1,2]-oxazine derivatives via annulations of aminoxy-tethered 1,7-enynes.

An efficient approach for the highly diastereoselective construction of functionalized cyclopenta[d][1,2]oxazines via sequential oxyamination and Pauson-Khand reaction of readily accessible propargylic alcohols has been developed. Furthermore, the ring closing metathesis of these N-O linked 1,7-enynes afforded vinylated-[1,2]oxazines in good yields. The reduction of the N-O bond of the obtained cyclopenta[d][1,2]oxazine is accomplished to access cyclopentenone-based amino alcohols.

Synthetic Access to Cyclopenta[a]inden-2(1H)-ones from Morita-Baylis-Hillman Products of 2-Alkynyl Benzaldehydes.

A new strategy for the synthesis of cyclopenta[a]inden-2(1H)-ones has been developed. An intramolecular Pauson-Khand reaction of the Morita-Baylis-Hillman (MBH) adducts, derived from 2-alkynyl benzaldehydes, provided the consequent novel cyclopenta[a]inden-2(1H)-ones bearing multifunctionalities including an ester group at the fused ring junction (tert-carbon center). The generality of this approach was illustrated by studying the several MBH derivatives containing diverse substitutions/functionalities.

One-Pot Consecutive Sulfonamidation/ipso-Cyclization Strategy for the Construction of Azaspirocyclohexadienones.

Harnessing of Morita-Baylis-Hillman (MBH) carbonates of acetylenic aldehydes as handy synthons has allowed a facile synthesis of azaspirocyclohexadienones by sequential DABCO-promoted sulfonamidation/ICl-mediated ipso-iodocyclization reactions. A variety of MBH-carbonates having aryl or heteroaryl groups on the alkyne functionality fruitfully participated in the one-pot ipso-annulation reaction to provide the corresponding 3-iodo spirocyclohexadienones. The sulphonamide functionality was further utilized to construct the tricyclic fused-sultam framework.

ipso-Cyclization: an emerging tool for multifunctional spirocyclohexadienones.

ipso-Annulation represents an attractive approach to synthesize a variety of spirocyclic compounds having a quaternary carbon center. Furthermore, these compounds also serve as a handy synthon for the construction of various complex molecules. This review presents various useful approaches for the intramolecular ipso-cyclization to afford a wide range of spirocyclohexadienones. In addition, the utility of spirocyclic compounds towards the synthesis of complex molecules is also included.

Total synthesis of a piperidine alkaloid, microcosamine A.

The first asymmetric total synthesis of a new natural piperidine alkaloid, microcosamine A, has been accomplished from d-serine and d-methyl lactate as chiral pool starting materials. Key features of the strategy include the utility of Horner-Wadsworth-Emmons reaction, Luche reduction, intramolecular carbamate N-alkylation to form the piperidine framework and Julia-Kocienski olefination to install the triene side-chain.