Diels-Alder reactions arylation, boron derivatives

Stable aryl boronates derived from tartaric acid catalyze the reaction of cyclo-pentadiene with vinyl aldehyde with high selectivity. Chiral acyloxy borane (CAB), derived from tartaric acid, has proved to be a very powerful catalyst for the enantioselective Diels-Alder reaction and hetero Diels-Alder reaction. Scheme 5 23 presents an example of a CAB 73 (R = H) catalyzed Diels-Alder reaction of a-bromo-a,/i-cnal 74 with cyclopentadiene. The reaction product is another important intermediate for prostaglandin synthesis. In the presence of... 

We have developed a stable CAB 2 (R = aryl) complex that can be prepared in situ by mixing tartaric acid derivative and arylboronic acid at room temperature. In contrast with 2, R = H, which is both air- and moisture-sensitive, the B-alkylated catalyst 2, R = aryl or alkyl, is stable and can be stored in closed containers at room temperature (Eq. 39). A solution of the catalyst (20 mol %) is effective in catalyzing the hetero Diels-Alder reaction of aldehydes with a Danishefsky diene to produce dihydro-pyrone derivatives of high optical purity (up to 98 % ee) (Eq. 40) [39]. The extent of asymmetric induction is largely dependent on the structure of the boronic acid. In general, bulky phenylboronic acid (R = 2,4,6-Me3CeH2, o-MeOC6H4) results in excellent asymmetric induction. 

Yamamoto and coworkers have also shown that a derivative of catalyst (5) in which the boron is bound to bulky aryl groups, such as catalyst (13), is capable of catalyzing the hetero Diels-Alder reaction between Danishefsky s diene and aldehydes and deliver the corresponding dihydropyrone derivatives in high enantioselectivity (Equation 3) [13]. 

Pyrone reacts readily as a diene in Diels-Alder additions, but the initial adduct often loses carbon dioxide, generating a second diene that then adds a second mole of the dienophile reaction with maleic anhydride, shown below, is typical - a monoadduct can be isolated, which under more vigorous conditions loses carbon dioxide and undergoes a second addition. When the dienophile is an alkyne, methyl propiolate for example, benzenoid products result from the expulsion of carbon dioxide. Primary adducts, which have not lost carbon dioxide, can be obtained from reactions conducted at lower temperatures under very high pressure or in the presence of lanthanide catalysts. A useful example is the reaction of 2-pyrone and substituted derivatives with alkynyl boronates leading to aryl boronates 2-pyrone itself reacts in 86% yield with trimethylsilylethynyl boronate. ... 

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