Furthermore, as an application, the synthesis of a nonnatural fluoro-pseudosporamide (42) was attempted using the fluorine-substituted compound 40 (Figure ). L-Proline derivative 12 and alkyne fragment 7 were introduced to 40 using a similar method as the synthesis route of micitide 982 (1), resulting in the formation of a cyclization precursor. Subsequently, utilizing the best conditions of Larock macrocyclization mentioned earlier (Scheme 2, Table ), the cyclization reaction was attempted, leading to the successful formation of the desired highly strained fluoro atrop-linkage in 42 with a yield of 30%. The atropisomerism of compound 42 was determined to be in the Sa conformation by its NOESY spectrum and DFT calculations (see the Supporting Information). It is also worth noting that 42 was obtained as a single atropisomer. The synthesis method combining C-H biarylation and Larock macrocyclization demonstrated its remarkable effectiveness in the synthesis of strained cyclic peptides with any biaryl linkage. Moreover, its capability to easily synthesize non-natural biaryl linkages is noteworthy.