Asymmetric total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B.

The asymmetric total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B was achieved in 6-7 steps using an easily accessible meso-cyclohexadienone derivative. The [6,6]-bicyclic decalin B-C ring and the all-carbon quaternary stereocenter at C-6 were prepared via a desymmetric intramolecular Michael reaction with up to 97% ee. The naphthalene diol D-E ring was constructed through a sequence of Ti(Oi-Pr)4-promoted photoenolization/Diels-Alder, dehydration, and aromatization reactions. This asymmetric strategy provides a scalable route to prepare target molecules and their derivatives for further biological studies.

A Unified Strategy To Construct the Tetracyclic Ring of Calyciphylline A Alkaloids: Total Synthesis of Himalensine A.

The synthetic approach to the core framework of the calyciphylline A-type Daphniphyllum alkaloids and total synthesis of himalensine A were described herein. Nitrone-induced 1,3-dipolar [3 + 2] cycloaddition was applied for the construction of A/C rings along with the all-carbon quaternary center. Pd-catalyzed enolate alkenylation and ring closing metathesis (RCM) were adopted to install the B/D rings to accomplish the [6,6,5,7] core framework. Nazarov reaction was utilized to install the F ring to complete the total synthesis of himalensine A.

An asymmetric graphene oxide film for developing moisture actuators.

Although Janus films of different compositions have been commonly utilized to develop moisture actuators due to the different capabilities of swelling in materials, a sole material with a distinct structural design is also able to provide moisture-actuation. In this study, we simply used graphene oxide (GO) to fabricate a sole GO film with an asymmetric structure which consisted of a wavy layer and a smooth layer. Due to the asymmetric structure and excellent hygroscopicity of the GO material, the asymmetric graphene oxide (AGO) film (2.5 × 0.5 cm2) was responsive to moisture and showed a maximum bending angle change of ≈1800° as the relative humidity (RH) changed. Compared with other reports about moisture actuators, the AGO film exhibited a superior bending capability. Furthermore, we propose a novel mechanism for moisture actuation of the AGO film based on our detailed observations, and a wavy structure has been introduced for showing great potential in bending deformation. Finally, the AGO film was used as a grabber to grab a leaf and it exhibited good capability to twine around a plastic rod. This work provides a novel pathway for the development of moisture-responsive materials for potential applications in robotics, artificial muscles and switches.

Synthetic studies on daphniglaucins.

The synthetic approach to the core framework of daphniglaucin-type Daphniphyllum alkaloids is described herein. The B-C ring was constructed via a Rh-catalyzed [3+2] cycloaddition. Continuous quaternary centers were installed through [3+2] cycloaddition and alkylation. The attempt to build the A-D ring motif using dipolar cycloaddition of azomethine ylides was extensively investigated.

Synthesis and biological evaluation of novel A-seco-taxoids derived from 1-deoxybaccatin VI.

Three novel nor-seco-taxoids 13, 15, 23 in which the A rings are cleaved but the B, C, and D rings are retained were prepared from 1-deoxybaccatin VI via its nor-dioxo derivative and their structures were confirmed by 1H NMR, 13C NMR and high resolution MS. Oxidative introduction of C-1 hydroxyl to 1-deoxybaccatin VI with oxidising agent KBrO3 and catalyst RuCl3 led to the dioxo derivative 6 and its structure is determined by X-ray crystallographic analysis. A-seco taxoids 13, 15, 23 with a C-13 ester linkage were tested for cytotoxic activity and all compounds showed no measurable cytotoxic activity against HCT-116 cell line. However, 1-deoxy-9a-dihydrotaxane analogue 4 semi-synthesised from 1-deoxybaccatin VI is 10-fold less cytotoxic than paclitaxel, indicating the indispensible nature of the A ring double bond for the bioactivity of paclitaxel.

Trends in applying C-H oxidation to the total synthesis of natural products.

Covering: 2006 to 2015C-H functionalization remains one of the frontier challenges in organic chemistry and drives quite an active area of research. It has recently been applied in various novel strategies for the synthesis of natural products. It can dramatically increase synthetic efficiency when incorporated into retrosynthetic analyses of complex natural products, making it an essential part of current trends in organic synthesis. In this Review, we focus on selected case studies of recent applications of C-H oxidation methodologies in which the C-H bond has been exploited effectively to construct C-O and C-N bonds in natural product syntheses. Examples of syntheses representing different types of C-H oxidation are discussed to illustrate the potential of this approach and inspire future applications.