Negishi-type coupling

Intramolecular allylations can also provide flve-membered rings with ease, and the entropic benefits facilitate additions to ketone substrates. For example, the allylic boronate 121, formed by a Negishi-type coupling between alkenyl... 

Utilization of stereodefined alkenylalanes or alkenylzirconium reagents in palladium-catalyzed cross-coupling reactions greatly enhances the versatility of Negishi-type coupling reactions. These organometallics are readily available by hydroalumi-nation, carboalumination, and hydrozirconation of alkynes, respectively. 

Zinc Derivatives Oxazoles and benzoxazoles can be lithiated in the 2-position by alkyllithium. In transmetallation of lithiated oxazole excess zinc dichloride gave the highest yield. The zincated substrates 106 and 107 were used in Negishi-type coupling (Scheme 45). Reactions of zincated oxazoles and benzoxazole with aryl halides all proceed well. A similar reaction sequence was used in the preparation of a 2-oxazolyl-substituted tricyclic structure 108. 

Zinc Derivatives. 2-(Benzopyran-4-yl)pyridine Al-oxide has been prepared from 2-chlorozinciopyridine 7V-oxide and benzopyran-4-yl triflate in a Negishi-type coupling from 2-chlorozinciopyridine N-oxide (Scheme 66). A five-fold excess of the the zincated pyridine A-oxide had to be used for optimal formation of the cross-coupled product 161. 

Zinc Derivatives. Direct zincation of 6-bromoxazolo[4,5-b]pyridmes can be effected using activated zinc (Scheme 69). The zincated species 164 and 165 from oxazolo[4,5- ]pyridin-2(3 0-ones or 2-phenyl- or 2-benzyloxyoxazolo[4,5-b]pyridmes were used in Negishi-type coupling in a one-pot reaction with benzyl bromide for the preparation of 6-benzyl derivatives. ... 

In addition, sp -halides can serve also as a starting point for Negishi-type coupling reactions. For example, Reformatzky-type propanoates can be activated using Zn-Cu couple, which in turn undergo Negishi coupling to yield the products in excellent yields (see Experimental Section) (cf. also p. 893). ... 

The compatibility of this Negishi-type coupling with other organometallic functionalities such as tin or boroir can advantageously be used for sequential coupling as shown in Scheme 5-116. 

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