Tandem Heck reaction-anion capture

Z-tamoxifen 403 tandem cyclization 290, 295 tandem Heck reaction-anion capture 253-4 tandem Heck reaction-phenoxide capture 253 tandem Heck reactions 251, 252-4 tandem intramolecular Heck-intermolecular Stille cross-coupling 255 taxol 140, 143,243,245 ( )-tazettine 146,234 telomerization 352 telomerization products 343, 345 template effect 140 teraconic anhydride 468 terminal acetylenes, synthesis of 216-20 terminal alkynes 6, 213 terminal 2,2-diorgano-l-aIkcnylboronates 51 terminal diynes 207 ternary complex 444 ternary coupling 177... 

For previous reports of tandem Heck reaction-anionic capture sequences, see (a) Grigg, R., Sridharan, V. and Xu, L.-H. (1995) Palladium-catalyzed cyclization-amination of allenes - effect of base on regioselectivity of formation of allylic amines. J. Chem. Soc., Chem. Commun., 1903 and references cited therein (b) Ma, S. and Negishi, E. (1995) Palladium-catalyzed cyclization of general route to common, medium, and large ring compounds via cyclic carbopaUadation. J. Am. Chem. Soc., 117, 6345-7 and references cited therein. 

Nuss and co-workers have demonstrated that a tandem Heck cyclization-anion capture process can access substructures related to vitamin D [58] and the neocarzinostatin chromophore (162) (Scheme 6-28) [59]. In a one-pot procedure, diiodide 159 was converted into dienediyne 160 in low yield. In this reaction, the alkyne undergoes Heck... 

Whereas Hegedus [335] and Danishefsky [336] were the first to discover a tandem Heck reaction from o-allyl-A -acryloylanilines leading to tricyclic pyrrolo[l,2-a]indoles or pyridino[l,2-a]indoles [336], it has been the fantastic work of Grigg to unleash the enormous potential of this chemistry. Grigg and his co-workers parlayed their Pd-catalyzed tandem polycyclization-anion capture sequence into a treasure trove of syntheses starting with IV-allyl-o-haloanilines [337-345], Diels-Alder and olefin metathesis reactions can be interwoven into the sequence or can serve as the culmination step, as can a wide variety of nucleophiles. An example of the transformation of 289 to 290 is shown below in which indole is the terminating nucleophile [340],... 

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