Bryan M. Gatehouse

Bio: Bryan M. Gatehouse is an academic researcher from Monash University, Clayton campus. The author has contributed to research in topics: Crystal structure & Denticity. The author has an hindex of 21, co-authored 92 publications receiving 1346 citations.

Stereochemistry of formation of α-(4–6η)-PdCl complexes from steroidal αβ-unsaturated ketones; X-ray crystal structure of the α-(4–6η) progesterone complex of pentane-2,4-dionatopalladium

Abstract: [6β-2H]- and [6α-2H]-Cholest-4-en-3-one react with palladium(II) chloride in dry tetrahydrofuran to give the α-(4–6η)-PdCl compound with highly stereoselective loss of the 6β-deuteron or proton; the α-stereochemistry-has been firmly established by a full X-ray structural analysis of the α-(4–6η)Pd(acac) derivative of progesterone (Hacac = pentane-2,4-dione).

Synthesis and X-ray crystal structure of fruticosonine, a novel indole alkaloid from a New Zealand Aristotelia sp. (elaeocarpaceae)

Abstract: The structure of fruticosonine, a new type of indole alkaloid from A. fruticosa, has been determined by X-ray crystallography and by synthesis.

Synthesis of precursors of C4 and C5 cumulenones

Abstract: Bicyclo[2.2.l]hept-5-en-2-one was condensed with 2,2-dimethyl-1,3-dioxan-4,6-dione in the presence of titanium tetrachloride/pyridine to yield 5-(bicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2-dimethyl-1,3- dioxan-4,6-dione (6a) which on pyrolysis at 520-560o/0.01 mm gave acetone, carbon dioxide, cyclopentadiene and butatrienone. In the same way 5-(7'-oxabicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2- dimethyl-1,3-dioxan-4,6-dione (6b) was prepared from 7-oxabicyclo[2.2.1]hept-5-en-2-one and on pyrolysis at 570o/0.01 mm it gave acetone, carbon dioxide, furan and butatrienone. Alkylation of 2-trimethylsiloxybicyclo[2.2.1]hepta-2,5 with phenylthiomethyl chloride with titanium tetrachloride as catalyst followed by condensation with 2,2-dimethyl-1,3-dioxan-4,6-dione gave an endo/exo mixture of 5-(3'-phenylthiomethylbicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2-dimethy 1-1,3-dioxan- 4,6-dione. The structure of the endo isomer was established by X-ray crystallography. Oxidation of the phenylthiomethyl compound with m-chloroperbenzoic acid yielded the sulfoxide which was converted by boiling in carbon tetrachloride into 5-(3'-methylenebicyclo[2.2.l]hept-5'-en-2'-ylidene)- 2,2-dimethyl-1,3-dioxan-4,6-dione (8). Preliminary studies on the fragmentation of compound (8) have shown that at 450o/0.01 mm it is converted into acetone, carbon dioxide and products showing ketene absorption at 2140 cm-1. The formation of pentatetraenone has not been established with certainty. The 3'-phenylsulfonylmethyl, phenylselenyl and methyl derivatives of (6a) are also described.

The dynamic stereochemistry of some dicarbonyl[phosphorus(III)](I,3-di-t-butyl-2 methoxyarene)chromium compounds. Evidence for restricted rotation about arene–substituent bonds, including an X-ray crystal structure of dicarbonyl(triphenylphosphine)(1,3-di-t-butyl-2-methoxybenzene)chromium

Abstract: Low-temperature1H n.m.r. spectra of a series of dicarbonyl(triphenylphosphine)(1,3-di-t-butyl-2-methoxyarene)chromium compounds exihibit dynamic behaviour which is interpreted in terms of kinetic restrictiln of rotation about the arene–methoxy bond, and similar behaviour is observed in a chelated aryl chromium analogue of these compounds; this explanation is supported by anX-ray crystal structure of dicarbonyl (triohenylphosphine)(1,3-di-t-butyl-2 methoxybenzene) chromium in which the O–CH3group is syn to the chromium.

X-Ray crystal structure of a new heteropolyanion, [P4W8O40]12–, with an X:M ratio of 1:2

Abstract: The structure of the first heteropolyanion, [P4W8O40]12–, with an X:M ratio of 1:2, has been determined from single crystal X-ray studies of the sodium salt; the idealized anion has 2m symmetry and consists of a shell of WO6 octahedra and PO4 tetrahedra made up of four PW2O13 groups linked by corner sharing and a sodium atom is situated in the centre of the polyanion.

Palladium-catalyzed cross-coupling reactions in total synthesis.

Abstract: In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Cascade reactions in total synthesis.

Abstract: The design and implementation of cascade reactions is a challenging facet of organic chemistry, yet one that can impart striking novelty, elegance, and efficiency to synthetic strategies. The application of cascade reactions to natural products synthesis represents a particularly demanding task, but the results can be both stunning and instructive. This Review highlights selected examples of cascade reactions in total synthesis, with particular emphasis on recent applications therein. The examples discussed herein illustrate the power of these processes in the construction of complex molecules and underscore their future potential in chemical synthesis.

The Diels--Alder reaction in total synthesis.

Abstract: The Diels-Alder reaction has both enabled and shaped the art and science of total synthesis over the last few decades to an extent which, arguably, has yet to be eclipsed by any other transformation in the current synthetic repertoire. With myriad applications of this magnificent pericyclic reaction, often as a crucial element in elegant and programmed cascade sequences facilitating complex molecule construction, the Diels-Alder cycloaddition has afforded numerous and unparalleled solutions to a diverse range of synthetic puzzles provided by nature in the form of natural products. In celebration of the 100th anniversary of Alder's birth, selected examples of the awesome power of the reaction he helped to discover are discussed in this review in the context of total synthesis to illustrate its overall versatility and underscore its vast potential which has yet to be fully realized.