I. Introduction 1485II. Scope of This Review 1485III. Transformations of Cyclobutane Derivatives inOrganic Syntheses1486A. Ring-Opening Reactions 1486B. Ring-Contraction Reactions 1493C. Ring-Expansion Reactions 14951. Five-Membered Rings 14952. Six-Membered Rings 15093. Seven-Membered Rings 15174. Eight-Membered Rings 15215. Nine-Membered Rings 1523IV. Transformations of Cyclobutane Derivatives inNatural Product Syntheses1524A. Ring-Opening Reactions 1524B. Ring-Expansion Reactions 15261. Five-Membered Rings 15262. Six-Membered Rings 15293. Seven-Membered Rings 15324. Eight-Membered Rings 1533V. Conclusion 1534VI. Acknowledgments 1534VII. References 1534

The application of cyclobutane derivatives in organic synthesis.

[Song, Zhen-Lei] Sichuan Univ, Key Lab Drug Targeting, Educ Minist, Dept Med Chem,W China Sch Pharm, Chengdu 610041, Peoples R China

Semipinacol rearrangement in natural product synthesis.

Quaternary carbon stereocenters are found in a broad range of organic compounds, including important bioactive natural products and medicinal agents. Given their ubiquity and the significant synthetic challenges they present, quaternary carbon stereocenters have long attracted great interest from synthetic organic chemists. Numerous efforts have been devoted to their construction, leading to a spectrum of strategies for creating stereogenic quaternary carbon centers. In this context, the semipinacol rearrangement has proven successful. In this extension of the pinacol rearrangement, the 1,2-carbon-to-carbon migration in a 1,2-diol has been expanded to include leaving groups other than the hydroxyl group.Over the past decade, our laboratory has explored the semipinacol rearrangement strategy for the stereoselective construction of quaternary carbon stereocenters. We have investigated various substrates, including 2,3-epoxy alcohols (also termed α-hydroxy epoxides), 2,3-aziridino alcohols, and allylic alcoh...

Stereoselective Construction of Quaternary Carbon Stereocenters via a Semipinacol Rearrangement Strategy

Metalated heterocycles and their applications in synthetic organic chemistry.

The title reaction is valuable for the difunctionalization of alkenes through simultaneous construction of a C—CF3 bond and a quaternary carbon center, and could provide a straightforward strategy for the preparation of α-quaternary β-trifluoromethyl ketone derivatives

Copper-catalyzed tandem trifluoromethylation/semipinacol rearrangement of allylic alcohols.

A general approach to the synthesis of enantiomerically pure spirocyclic α,β-butenolides is presented where the fundamental framework is rapidly elaborated by acid- or bromonium ion-induced rearrangement of the carbinol derived by addition of 2-lithio-4,5-dihydrofuran to cyclobutanone. Subsequent resolution of the resulting ketones by either sulfoximine or mandelate acetal technology has been applied effectively. The availability of these building blocks makes possible in turn the acquisition of the enantiomers of dihydrofurans typified by 17, 35, and 38 and lactones such as 25 and 31, as well as the targeted title compounds. Complementary reductions of the early intermediates provide the added advantage that the α- and β-stereoisomeric carbinol series can be obtained on demand. These capabilities have been coordinated to allow the crafting of any member of the series in relatively few steps.

1-Oxaspiro[4.4]nonan-6-ones. Synthetic Access via Oxonium Ion Technology, Optical Resolution, and Conversion into Enantiopure Spirocyclic α,β-Butenolides

Spirocyclic restriction of nucleosides. An analysis of protecting group feasibility while accessing prototype anti-1-oxaspiro[4.4]nonanyl mimics.

Resolution and Absolute Configurational Assignments to 1-Oxa- and 1-Thia-6-ketospiro[4,4]nonanyl Platforms

1-Oxaspiro[4.4]nonan-6-ones. Synthetic Access via Oxonium Ion Technology, Optical Resolution, and Conversion into Enantiopure Spirocyclic α,β-Butenolides.

Dafydd R. Owen

Papers

1-Oxaspiro[4.4]nonan-6-ones. Synthetic Access via Oxonium Ion Technology, Optical Resolution, and Conversion into Enantiopure Spirocyclic α,β-Butenolides

Spirocyclic restriction of nucleosides. An analysis of protecting group feasibility while accessing prototype anti-1-oxaspiro[4.4]nonanyl mimics.

Resolution and Absolute Configurational Assignments to 1-Oxa- and 1-Thia-6-ketospiro[4,4]nonanyl Platforms

1-Oxaspiro[4.4]nonan-6-ones. Synthetic Access via Oxonium Ion Technology, Optical Resolution, and Conversion into Enantiopure Spirocyclic α,β-Butenolides.