S1 Supporting Information Pd(II)-Catalyzed Asymmetric Approach toward Chiral [3.3.1]-Bicyclic Ketals Using 2-Hydroxyphenylboronic Acid as a Pro-bis(nucleophile) Feijun Wang, *,† Feng Chen, † Mingliang Qu, † Teng Li, † Yunlong Liu, † and Min Shi *,†,‡ 1 Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, and 130 MeiLong Road, Shanghai 200237, People’s Republic of China, and 2 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, People’s Republic of China feijunwang@ecust.edu.cn, Mshi@mail.sioc.ac.cn CONTENTS General remarks…………………………………………………………………………………………..S2 The procedure for the preparation of ketal 4aa.…………………….....……………………..…………...S3 Optimization of reaction conditions…………………………………………………………..…………..S4 General procedure for the Pd(II)-catalyzed asymmetric cascade reaction…………………..…………..S5 Characterization data and chiral HPLC analysis of [3.3.1]-bicyclic ketal 4……………...…………..…S6 Characterization data of [D]-3al and [D]-4al, and chiral HPLC analysis of [D]-4al………………..…S67 Characterization data and chiral HPLC analysis of spiroketal 6………………………….…………..…S70 References……………………………………………………………………………………………..…S72 X-ray crystal data of ketal 4aa………………………………………………………………………….S73 X-ray crystal data of ketal (6S,12S)-4ia………………………………………………………………...S74 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013