TTMPP

In the coupling of the allenyl ester 7 with a terminal alkyne, an electron-deficient phosphine (Ph3P) gave the enyne-conjugated ester 8 as the major product, while an electron-rich phosphine (TDMPP or TTMPP) yielded the non-conjugated enyne esters ( )- and (Z)-9[4],... 

Styrene and 1-decene are selectively epoxidized, as shown in Table XXVII (293). The rates observed for PWM-Co are greater than those observed for Ni(dmp)2 and Fe(dmp)3, and the selectivities are comparable or higher for the former (295). It is also remarkable that PWn—Co polyanion exhibits a steric effect comparable to that of a moderately hindered TTMPP ligand in the... 

Strong Lewis bases such as tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) and DBLf (1) can catalyse the transformation of cinnamaldehyde to saturated carboxylic acids, whereas mild bases such as triphenylphosphine or tris(4-methoxyphenyl)phosphine give simple cyanohydrin products [85]. When quenching the reaction with alcohol and amine, the corresponding ester and amide are produced, respectively (Scheme 3.44). 

Contra-Peterson elimination also occurred in Morita-Baylis-Hillman-type reactions of 1-silylcyclopropene 101. Addition of the nucleophilic catalyst tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) at the 2-position of the alkene and condensation of the anion with an aldehyde led to 1,3-Brook rearrangement, with expulsion of the catalyst to regenerate the cyclopropene double bond in product 102. ... 

Likewise, subjection of o-alkynyltrifluoroacetanilides to benzyl bromide in the presence of Pd2(dba)3 and ttmpp in THF furnishes 3-benzyl indoles (Scheme 24). 

Subjection of these A-allyl derivatives to Pd(PPh3)4 and K2CO3 in MeCN at 90 °C or Pd2(dba)3 and ttmpp in DME at 100 °C produces 2-substituted 3-allylindoles in good to high yield (Scheme 27). 2-Unsubstituted 3-allylindoles have also been prepared, albeit... 

Substituted 3-allylindoles can also be prepared through a third procedure that is based on the reaction of o-alkynyltrifluoroacetanilides with aUyl carbonates in the presence of the Pd2(dba)3-ttmpp catalyst system in THF at 60 °C and that apparently does not involve 7V-allyl intermediates (Scheme 29). 

As to the process that affords 3-allylindoles without the intermediacy of an Al-allyl derivative, a possible explanation considers the reaction of the o-alkynyltrifluoroac-etanilide with the rj -allylpalladium intermediate derived from the allyl carbonate. The strongly basic sterically encumbered ligand ttmpp might control the reactivity of the latter so as to favor the formation of the rj -alkyne-Tj -allylpalladium complex via coordination of the alkyne moiety to the palladium (Scheme 31a) at the expense of the nucleophilic attack of the nitrogen on the aUytic fragment, which would lead to the formation of the A-allyl product (Scheme 31b). 

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