Stereoselective Synthesis of Allenyl Alcohols by Cobalt(III)-Catalyzed Sequential C-H Bond Addition to 1,3-Enynes and Aldehydes

An efficient and stereoselective Co-III-catalyzed sequential C-H bond addition to 1,3-enynes and aldehydes is disclosed. This transformation represents the first example of sequential C-H bond additions to 1,3-enynes and a second coupling partner and provides the first example of preparing allenes by C-H bond addition to 1,3-enynes. A wide range of aldehydes, C-H bond substrates and 1,3-enynes with large substituents on the alkynes are effective substrates. The allenyl alcohol products can be further converted to dihydrofurans with high stereoselectivity either in situ or under Ag-mediated cyclization conditions. The allenyl silyl group can also be transferred to the adjacent alcohol by a Brook rearrangement. Moreover, a mechanism for the transformation is proposed supported by X-ray structural characterization of a cobaltacycle intermediate.

Automated summary

An efficient and stereoselective Co-III-catalyzed sequential C-H bond addition method to 1,3-enynes and aldehydes is reported, providing a new way to prepare allenyl alcohol products. The mechanism of this transformation is proposed and supported by the X-ray structural characterization of a cobaltacycle intermediate.