Preface

The proposal of this book entitled Addition Reactions with Unsaturated Hydrocarbons was approved by Wiley-VCH GmbH in November 2015. It was expected to be published after two years; however, it took me much more time to finish the writing work because of the recent great development of chemistry in fundamental studies and applications of unsaturated hydrocarbons, and an enormous amount of literature must be read.

Modern synthetic methods require to be green procedures with atom/step economy and high chemo-/regio-/stereoselectivity, and the addition and cycloaddition reactions of unsaturated hydrocarbons such as alkynes [1], alkenes [2], allenes [3], enynes, and diynes [4] are showing great advances in these features, which have been well developed and applied in the synthesis of carbo- and heterocycles [5], in the construction of challenging skeletons of complex molecules and polymers [6], and other transformations [7].

This book contains 10 chapters and is devoted mainly to detailed introduction and discussions of the reactions of unsaturated hydrocarbons as the versatile building blocks in a wide variety of important organic synthesis. Chapters 1 and 2 describe the homo- and cross-dimerization of alkynes and alkenes, the addition reactions of C(sp)-H bond to unsaturated compounds to give enynes, and alkynylated compounds, which are also important unsaturated hydrocarbons for further transformations. Chapters 3 and 4 summarize the recent development of hydrofunctionalization of alkynes and alkenes to provide the atom economic approach to functionalized alkenes and alkanes. Chapters 5 and 6 describe the double functionalization of alkynes and alkenes by addition reactions of element-element bonds or carbon-element bonds. Chapters 7 and 8 include a number of annulations or cycloadditions of alkynes and alkenes for the synthesis of carbocycles and heterocycles in one-pot reactions. In addition, Chapter 9 summarizes the synthesis of carbonyl compounds from the hydration of alkynes, the addition reactions of alkynes and alkenes with carbonyl compounds, and the carbonylation of alkynes and alkenes with carbon monoxide. Finally, in Chapter 10, it introduces a few examples of the reported procedures on the synthesis of natural products involving alkyne transformation as the key step. More than 600 schemes are shown to describe the typical reactions starting from unsaturated hydrocarbons, and over 3600 literatures are cited, including about 500 review papers to allow greater access to more original papers for readers.

The new chemistry of unsaturated hydrocarbons will continue to grow and expand because of their numerous and apparently endless applications to develop the efficient synthetic methodologies for the synthesis of a vast array of chemicals. I believe this book has a comprehensive coverage of important and up-to-date reactions of unsaturated hydrocarbons, and it is hoped that the book will play multiple-purpose usage for students and chemists in both the universities and industrial laboratories.

Tsinghua University
Beijing, China

Dr. Ruimao Hua

References

Selected review papers on the applications of the addition and cycloaddition reactions of unsaturated hydrocarbons.

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4. 4 (a) García-Rubín, S., Varela, J.A., Castedo, L., and Saá, C. (2008). Recent advances in "formal" ruthenium-catalyzed [2?+?2?+?2] cycloaddition reactions of diynes to alkenes. Chem. Eur. J. 14: 9772-9778.(b) Aubert, C., Fensterbank, L., Garcia, P. et al. (2011). Transition-metal-catalyzed cycloisomerizations of 1,n-allenynes and -allenenes. Chem. Rev. 111: 1954-1993.(c) Raviola, C., Protti, S., Ravelli, D., and Fagnoni, M. (2016). (Hetero) aromatics from dienynes, enediynes and enyne-allenes. Chem. Soc. Rev. 45: 4364-4390.(d) Xuan, J. and Studer, A. (2017). Radical cascade cyclization of 1,n-enynes and diynes for the synthesis of carbocycles and heterocycles. Chem. Soc. Rev. 46: 4329-4346.(e) Babazadeh, M., Soleimani-Amiri, S., Vessally, E. et al. (2017). Transition metal-catalyzed [2?+?2?+?2] cycloaddition of nitrogen-linked 1,6-diynes: a straightforward route to fused pyrrolidine systems. RSC Adv. 7: 43716-43736.(f) Xu, C.-H., Li, Y., Li, J.-H. et al. (2019). Recent advances in radical-mediated [2?+?2?+?m] annulation of 1,n-enynes. Sci. Chin. Chem. 62: 1463-1475.
5. 5 (a) Schore, N.E. (1988). Transition metal-mediated cycloaddition reactions of alkynes in organic synthesis. Chem. Rev. 88: 1081-1119.(b) Welker, M. (1992). [3?+?2] Cycloaddition reactions of transition-metal 2-alkynyl and ?1-allyl complexes and their utilization in five-membered-ring compound syntheses. Chem. Rev. 92: 97-112.(c) Cacchi, S. (1999). Heterocycles via cyclization of alkynes promoted by organopalladium complexes. J. Organomet. Chem. 576: 42-64.(d) Yet, L. (2000). Metal-mediated synthesis of medium-sized rings. Chem. Rev. 100: 2963-3008.(e) Belmont, P. and Parker, E. (2009). Silver and gold catalysis for cycloisomerization reactions. Eur. J. Org. Chem. 2009: 6075-6089.(f) Hua, R., Abrenica, M.V.A., and Wang, P. (2011). Cycloaddition of alkynes: atom-economic protocols for constructing six-membered cycles. Curr. Org. Chem....