C-H Insertion on sulfonyl compounds Synthesis of Plakortethers Petroleum products are an excellent source of relatively simple organic compounds. Developments of methods for their diversification provides synthetic intermediates that can be used in the synthesis of biologically active natural products. C-H Insertion on sulfonyl compounds Synthesis of Plakortethers Studies on selectivity and scope R1 R2 R3 R4 Cat Product 2 Product 3 Me Me H H Rh2(OAc)4 55% - Me H H H 60%, dr 5:1 ~3%1 Me H H H Rh2(esp)2 70%, dr 2:1 Rh2(pfb)4 25%, dr 1:1 52%1 H H H H ~2%1 28%1 Not detected 60%1 Me H Me H 50%, dr >10:12 20%1 ~5%1 60%1,dr >10:12 Me H Me Me 80%1 Rh2(MEPY)4 50%, ee 2%3 Rh2(DOSP)4 45%, ee 20%3 Rh2(PTTL)4 55%, ee 50%3 1 Combined for both diastereomers 2 At the b-carbon 3 For the trans-diastereomer Conclusion: Identified catalysts and structural features that influence preference for formation of 6 and 5 membered rings. Synthetic transformations Studies on the synthesis of Terpiodiene Alkylation R1 R2 n X E+ Yield Me Me 2 CH2 Allyl bromide 95% EtI 80% Me H 2 CH2 90%, single diastereomer BnBr 95%, single diastereomer Me Me 2 O 85% Me H 1 CH2 C-S bond scission