A facile stereoselective synthesis of difunctionalized 1,3-dienes containing tin and halogen via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes

Cai, Mingzhong; Wang, Yue; Wang, Pingping

doi:10.1016/j.jorganchem.2008.06.002

Cited by 9 publications

(2 citation statements)

References 51 publications

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“…[17] Recently, we described the stereoselective synthesis of (Z,Z)-2-silyl-3-stannyl-substituted 1,3-dienes through the hydromagnesiation of alkynylsilanes, followed by crosscoupling with (E)-α-iodovinylstannanes catalyzed by Pd(PPh 3 ) 4 [18] and the stereoselective synthesis of difunctionalized 1,3-dienes containing tin and halogen by hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes. [19] However, to the best of our knowledge, no well-established method has been used to prepare stereoselectively (1E,3E)-1-sulfonyl-3-(tributylstannyl)-substituted 1,3-dienes. Herein, we wish to report that (1E,3E)-1-sulfonyl-3-(tributylstannyl)-substituted 1,3-dienes could be conveniently synthesized by the cis addition of terminal alkynes to acetylenic sulfones in the presence of a catalytic amount of palladium acetate and tri(2,6-dimethoxyphenyl)phosphane (2,6-TDMPP), followed by palladium-catalyzed hydrostannylation with tributyltin hydride (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

Zhao¹,

Yang²,

Xie³

et al. 2011

Eur J Org Chem

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Using palladium‐catalyzed addition reactions, a terminal alkyne, an acetylenic sulfone, and a tin hydride comprise the building blocks for the construction of difunctionalized 1,3‐dienes containing tin and sulfonyl groups in an atom‐economical fashion. Terminal alkynes 1 undergo clean cis addition to acetylenic sulfones 2 in the presence of catalytic amounts of palladium acetate and tri(2,6‐dimethoxyphenyl)phosphane to give (E)‐1‐sulfonyl‐substituted 1,3‐enynes 3 in excellent yields. Hydrostannylation of 1,3‐enynes 3 with tributyltin hydride in the presence of Pd(PPh3)4 affords regio‐ and stereoselectively (1E,3E)‐1‐sulfonyl‐3‐tributylstannyl‐substituted 1,3‐dienes 4 in excellent yields.

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Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

Zhao¹,

Yang²,

Xie³

et al. 2011

Eur J Org Chem

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“…Vinyl halides, in particular, are versatile substrates in many useful organic transformations including the well-known Stille, Suzuki, and Sonogashira coupling reactions [4][5][6][7][8][9][10]. The importance of vinyl halides in organic synthesis has stimulated a great deal of interest and much attention has been devoted to the synthesis of vinyl halides and their derivatives [11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

Xie¹,

Wang²,

Zhang³

et al. 2009

Journal of Organometallic Chemistry

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Hydrozirconation of Alkynes

Milligan,

Hammill,

Crocker

et al. 2023

Organic Reactions

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Since the first preparation of organozirconocenes from alkenes and alkynes in 1972, hydrozirconation has become one of the most commonly used stoichiometric methods to convert readily available starting materials into reactive but stable organometallic intermediates. A broad range of subsequent transformations may be employed to convert organozirconocenes in situ into high‐value functionalized products, often with the strategic formation of one (or several) new carbon–carbon bonds. This chapter focuses on the hydrozirconation of terminal and internal alkynes, and the subsequent synthetic transformations of the resulting alkenylzirconocenes. Zirconocene hydrochloride, Cp 2 Zr(H)Cl, is most frequently employed for the hydrozirconation step and can be used as a reagent or prepared in situ. Subsequent reactions of alkenylzirconocenes include additions to inorganic electrophiles such as halogens, as well as in situ ligand transfers to other metals, such as palladium and zinc, that further expand the range of accessible bond formations. The initial discussion focuses on the mechanism and stereochemical considerations, and on the steric and electronic factors that determine the regiochemistry of the either kinetically or thermodynamically controlled hydrozirconation. The “Scope and Limitations” section presents information on functional group compatibilities and is organized by the type of synthetic transformation of alkenylzirconocenes. Representative applications of the hydrozirconation of alkynes are showcased in syntheses of natural products, comparisons to alternative methods for the hydrometallation of alkynes. The goal of this chapter is to demonstrate the significance of hydrozirconation in organic synthesis, including the utility of the stoichiometric zirconium organometallics obtained from alkyne substrates, and to provide inspiration for the future development of new synthetic methods and strategies.

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A facile stereoselective synthesis of difunctionalized 1,3-dienes containing tin and halogen via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes

Cited by 9 publications

References 51 publications

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

Hydrozirconation of Alkynes

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