The alkoxycarbonylating carbamates 1 and 2 are readily prepared and reacted under mild conditions with polyfunctional substrates, eg amino acids, unsymmetrical diols, and unprotected carbohydrates (D-glucosamine and methyl or-D-glucoside), thus affording carbamatcs or monocarbonates in good yields and with high chemo-and regioselectivity.