83021-59-4

Upstream product

• 591-50-4 iodobenzene 
• 91083-32-8 <(Z)1-Bromo-1-hexenyl>diisopropoxyborane 
• 917-54-4 methyllithium 
• 29541-98-8 pentylidenetriphenylphosphorane 
• 98-86-2 acetophenone 
• 17763-67-6 Phenyl triflate 
• 131534-66-2 diisopropyl [(Z)-(2-hepten-2-yl)]boronate 

Downstream Products

• 7661-44-1 2-phenyl-3-heptanone 

Relevant academic research and scientific papers

Spiro[1,2]oxaphosphetanes of nonstabilized and semistabilized phosphorus ylide derivatives: Synthesis and kinetic and computational study of their thermolysis

A series of tri- and tetrasubstituted spiro-oxaphosphetanes stabilized by ortho-benzamide (oBA) and N-methyl ortho-benzamide (MoBA) ligands have been synthesized by the reaction of Cα,Cortho-dilithiated phosphazenes with aldehydes and ketones. They include enantiopure products and the first example of an isolated oxaphosphetane having a phenyl substituent at C3 of the ring. Kinetic studies of their thermal decomposition showed that the process takes place irreversibly through a polar transition state (ρ = -0.22) under the influence of electronic, [1,2], [1,3] steric, and solvent effects, with C3/P-[1,2] interactions as the largest contribution to ΔG of olefination. Inversion of the phosphorus configuration through stereomutation has been observed in a number of cases. DFT calculations showed that oBA derivatives olefinated through the isolated (N, O)(Ph, C6H4, C) oxaphosphetanes (Channel A), whereas MoBA compounds decomposed faster via the isomer (C6H4, O)(C, N, Ph) formed by P-stereomutation involving a MB2 permutational mechanism (Channel B). The energy barrier of P-isomerization is lower than that of olefination. Fragmentation takes place in a concerted asynchronous reaction. The thermal stability of oxaphosphetanes is determined by strong C3/P-[1,2] interactions destabilizing the transition state of olefination. The effect of charge distribution and C3/C4-[1,2] and C4/P-[1,3] steric and solvent interactions on ΔG was also evaluated.

Polymer-bound palladium-catalyzed cross-coupling of organoboron compounds with organic halides and organic triflates

The polymer-bound palladium-catalyzed cross-coupling reaction of electrophiles (i.e., halides and triflates) with oganoboron compounds to form carbon-carbon bonds was achieved at mild conditions with very high activity in the Suzuki coupling reaction. The polymeric catalyst can be easily separated from a reaction mixture and reused more than 10 times with no decrease in activity.

Palladium-Catalyzed Cross-Coupling Reaction of Organoboron Compounds with Organic Triflates

The cross-coupling reaction of 9-alkyl-9-borabicyclononane (9-R-9-BBN), 1-alkenyl-1,3,2-benzodioxaborole, or aryl boronic acid with 1-alkenyl or aryl triflates in the presence of K3PO4 (1.5 equiv) and a catalytic amount of Pd(PPh3)4 or Cl2Pd(dppf) resulted in high yields.The reaction conditions are sufficiently mild so that a variety of functionalized alkenes, alkadienes, and arenes are readily obtained.The utility of the present reaction was demonstrated by the cyclization of ω-alkenyl triflates leading to a benzo-fused cycloalkene and bicyclic alkene via a hydroboration intramolecular coupling sequence.

Stereo- and Regiospecific Synthesis of Trisubstituted Alkenes via the Palladium-catalyzed Cross-coupling Reaction of Diisopropyl (E)-(1-Alkyl-1-alkenyl)boronates with Organic Halides

The reaction of diisopropyl (Z)-(1-bromo-1-alkenyl)boronates readily obtainable, with organolithiums and bases takes place readily to give (E)-(1-organo-1-alkenyl)boronates, the cross-coupling of which with various organic halides proceeds smoothly in the presence of Pd-catalyst and base to afford stereodefinied trisubstituted alkenes in good yields.