Oxidative addition of very robust C−F and C− O bonds has been accomplished in reactions of the aluminum(I) compound NacNacAl (1, NacNac = [ArNC-(Me)CHC(Me)NAr] − and Ar = 2,6-Pr i2 C 6 H 3 ) with fluoroarenes, fluoroalkanes, and ethers. Similar to the transition metals, the ease of aryl C−F oxidative addition decreases as the degree of fluorination diminishes on the aromatic substrate. As well, kinetic studies on the addition of 1,2,3,4-tetrafluorobenzene to compound 1 revealed a second-order reaction characterized by a very negative entropy of activation (ΔS ⧧ = −113.6(3) J/K•mol), consistent with a transition metal-like oxidative addition process.

The aluminum(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis(phenyl sulfide) complex NacNacAl(SPh)2 (2) and alkyl thiolate aluminum complex NacNacAlEt(SEt) (3). As well, reaction of 1 with tetraphenyl diphosphine furnishes the bis(diphenyl phosphido) complex NacNacAl(PPh2)2 (4). Production of 3 and 4 are the first examples of C(sp(3))-S and R2P-PR2 activation by a main-group element complex. All three complexes were characterized by multinuclear NMR spectroscopy and X-ray crystal structure analysis. Furthermore, a variable-temperature NMR spectroscopic study was undertaken on 4 to study its dynamic behavior in solution.

This review explores the strategies and tactics of effective dearomative retrosynthetic logic, illustrated through numerous outstanding examples of contemporary natural product total synthesis.

Simple three-step asymmetric and racemic syntheses of GlaxoSmithKline's highly potent PDE IVb inhibitor 1 were developed. The suggested approach is based on reductive domino transformations of 3-β-carbomethoxyethyl-substituted six-membered cyclic nitronates, which are easily accessed by a stereoselective [4 + 2] cycloaddition of an appropriate nitroalkene to vinyl ethers. In vitro studies of PDE IVb inhibition by enantiomeric pyrrolizidinones (+)-1 and (-)-1 were performed.

The isomalabaricanes comprise a large family of marine triterpenoids with fascinating structures that have been shown to be selective and potent apoptosis inducers in certain cancer cell lines. In this article, we describe the successful total syntheses of the isomalabaricanes stelletin A, stelletin E, and rhabdastrellic acid A, as well as the development of a general strategy to access other natural products within this unique family. High-throughput experimentation and computational chemistry methods were used in this endeavor. A preliminary structure−activity relationship study of stelletin A revealed the trans-syn-trans core motif of the isomalabaricanes to be critical for their cytotoxic activity.